Hair dyeing process using at least one direct and/or natural dye, a titanium salt, a cellulose-based polysaccharide and optionally a particular organic solvent

ABSTRACT

The present invention relates to a process for dyeing keratin fibres, in particular human keratin fibres such as the hair, in which said fibres are treated using one or more cosmetic compositions comprising a) one or more dyes chosen from synthetic direct dyes and dyes of natural origin, b) one or more titanium salts and b1) optionally one or more particular carboxylic acids, c) one or more cellulose-based polysaccharides, d) optionally one or more organic compounds that are liquid at 25° C., with a Hansen solubility parameter value δH&lt;16 (MPa) 1/2  at 25° C., e) optionally one or more chemical oxidizing agents such as hydrogen peroxide or one or more hydrogen peroxide-generating systems.

The present invention relates to a process for dyeing keratin fibres, inparticular human keratin fibres such as the hair, in which said fibresare treated using one or more cosmetic compositions comprising a) one ormore synthetic direct dyes and/or dyes of natural origin, b) one or moretitanium salts and b1) optionally one or more particular carboxylicacids, c) one or more cellulose-based polysaccharides, d) optionally oneor more organic compounds that are liquid at 25° C., with a Hansensolubility parameter value δH<16 (MPa)^(1/2) at 25° C., e) optionallyone or more chemical oxidizing agents such as hydrogen peroxide or oneor more hydrogen peroxide-generating systems.

It is known practice to dye keratin fibres and in particular human hairwith dye compositions containing direct dyes. The standard dyes that areused are, in particular, dyes of the nitrobenzene, anthraquinone,nitropyridine, azo, xanthene, acridine, azine or triarylmethane type, ornatural dyes.

These dyes may be nonionic, anionic, cationic or amphoteric. These dyesare coloured or colouring molecules that have affinity for keratinfibres. These compositions containing one or more direct dyes areapplied to keratin fibres for a time necessary to obtain the desiredcolouring, and are then rinsed out. The colourings that result therefromare particularly chromatic colourings but are, however, only temporaryor semi-permanent since the nature of the interactions that bind thedirect dyes to the keratin fibre and their desorption from the surfaceand/or the core of the fibre are responsible for their weak dyeing powerand their poor persistence with respect to light, washing orperspiration.

Progress therefore remains to be made in this field in order to affordpowerful, resistant dyeing results that respect the nature of the hairusing compositions containing dyes that are especially natural.

In the field of dyeing using natural extracts such as ortho-diphenols(ODPs), it is also known practice to dye keratin materials such as thehair or the skin using ODPs in the presence of a metal salt especiallyof manganese (Mn) and/or zinc (Zn). In particular, patent applicationsFR 2 814 943, FR 2 814 945, FR 2 814 946 and FR 2 814 947 proposecompositions for dyeing the skin or keratin fibres, comprising a dyeprecursor that contains at least one ortho-diphenol, Mn and/or Zn oxidesand salts, alkaline agents of hydrogen carbonate type in a particularMn, Zn/hydrogen carbonate ratio and optionally an enzyme. According tothese documents, it is possible to obtain colourings of keratinmaterials with atmospheric oxygen or any oxygen-generating system.

However, the colourings obtained using ODPs are not strong enough orintense enough, and/or are not very persistent, especially in the caseof hair fibres.

It is known practice to use metals at acidic pH for dyeing keratinfibres in amounts similar to those employed for dyes using a mordantingprocess, which consists in preparing the fibres before performing thedyeing operation in order to obtain persistent shades (Ullmann'sEncyclopaedia “Metal and Dyes”, 2005 §5.1, p. 8). However, this processgenerally has the drawback of not always respecting the cosmetic natureof the keratin fibre.

Other documents describe the use of ODPs in combination with Mn and Znsalts and other metal salts, including titanium salts, and a chemicaloxidizing agent (FR 297 673, WO2011/086284, WO2011/086282 and FR 2 951374).

Nevertheless, improvements should be further made, especially in termsof persistence of the colour with regard to shampooing and to sweat.

There is thus a real need to develop dyeing processes that make itpossible to obtain more powerful and/or more persistent colourings usingsynthetic direct dyes and/or dyes of natural origin, in particular ODPs,preferably using natural extracts that are rich in ODPs, less aggressiveto keratin fibres, or that require smaller amounts of dyes. Moreparticularly, there is a need to obtain colourings that satisfactorilywithstand external agents (light, bad weather, shampooing or sweat),which are persistent and homogeneous, i.e. showing little dyeingselectivity between the root and the end, while at the same timeremaining strong and/or chromatic. In addition, it is necessary, inorder to obtain satisfactory dyeing performance, for the product to bestable and to have suitable working qualities, i.e. a sufficientrheology so as not to run during the leave-on time. For this, it ispreferable for the dye support not to interact in the dyeing process.

This (these) aim(s) are achieved by the present invention, one subjectof which is a process for dyeing keratin fibres, in particular humankeratin fibres such as the hair, in which said fibres are treated, inone or more steps, with one or more cosmetic compositions containing,taken together or separately in said composition(s), the followingingredients:

-   a) one or more dyes chosen from synthetic direct dyes and dyes of    natural origin, preferably chosen from ODPs;-   b) one or more titanium salts; in particular, the Ti atom of the    salt is of oxidation state 2, 3 or 4, denoted Ti(II), Ti(III) or    Ti(IV), preferably Ti(IV);-   b1) optionally one or more carboxylic acids of formula (I) below:

formula (I) or a salt thereof, in which:

-   -   A represents a saturated or unsaturated, cyclic or non-cyclic        and aromatic or non-aromatic hydrocarbon-based group, which is        monovalent when n has the value 0 or polyvalent when n is        greater than or equal to 1, comprising from 1 to 50 carbon        atoms, which is optionally interrupted with one or more        heteroatoms and/or optionally substituted, especially with one        or more hydroxyl groups; preferably, A represents a monovalent        (C₁-C₆)alkyl group or a polyvalent (C₁-C₆)alkylene group        optionally substituted with one or more hydroxyl groups;    -   n represents an integer between 0 and 10 inclusive; preferably,        n is between 0 and 5, such as between 0 and 2;

-   c) one or more cellulose-based polysaccharides;

-   d) optionally one or more organic compounds that are liquid at    25° C. with a Hansen solubility parameter value δH of less than 16    (MPa)^(1/2) at 25° C.; and

-   e) optionally one or more chemical oxidizing agents chosen in    particular from hydrogen peroxide or one or more hydrogen    peroxide-generating systems.

Preferably, the composition(s) used in the process of the invention areaqueous.

Another subject of the invention is a cosmetic composition comprisingingredients a), b), c), optionally d) and optionally e), as definedpreviously.

Another subject of the present invention relates to a multi-compartmentdevice comprising ingredients a), b), c), optionally d) and optionallye), distributed in several compartments.

The multi-compartment device or “kit” is suitable for performing thedyeing process according to the invention.

The process according to the invention has the advantage of dyeing humankeratin fibres, with persistent dyeing results. In particular, thedyeing process according to the invention can produce colourings thatare resistant to washing, perspiration, sebum and light withoutimpairing the fibres. The resistance to perspiration is particularlygood. Furthermore, the dyeing process used can induce a satisfactory“build-up” and/or strength of the colouring.

Other subjects, characteristics, aspects and advantages of the presentinvention will emerge even more clearly on reading the description andthe examples that follow.

a) Dye(s)

In accordance with the present invention, the dyeing process uses a) oneor more synthetic direct dyes and/or dyes of natural origin.

The dye(s) of the invention may be present in one or more cosmeticcompositions used during the dyeing process.

According to a particular embodiment of the invention, the dye(s) arechosen from synthetic direct dyes.

The synthetic direct dye(s) that may be used in the context of theinvention may be chosen from fluorescent or non-fluorescent, anionic,cationic or neutral direct dyes.

These synthetic direct dyes are chosen in particular from thoseconventionally used in direct dyeing, any commonly used aromatic and/ornon-aromatic dyes such as neutral, acidic or cationic nitrobenzenedirect dyes, neutral, acidic or cationic azo direct dyes, natural directdyes, neutral, acidic or cationic quinone and in particularanthraquinone direct dyes, azine, polyarylmethane such astriarylmethane, indoamine, polymethine such as styryl, porphyrin,metalloporphyrin, phthalocyanine, methine cyanine direct dyes.

According to a particular embodiment of the invention, the dye(s) arechosen from anionic direct dyes. These dyes are commonly referred to as“acidic” direct dyes or “acid dyes” on account of their affinity foralkaline substances. The term “anionic direct dyes” means any direct dyecomprising in its structure at least one CO₂R or SO₃R substituent with Rdenoting a hydrogen atom or a cation originating from a metal or anamine, or an ammonium ion. The anionic dyes may be chosen from acidicnitro direct dyes, acidic azo dyes, acidic azine dyes, acidictriarylmethane dyes, acidic indoamine dyes, acidic anthraquinone dyes,indigoid dyes and acidic natural dyes.

According to another particular embodiment of the invention, the dye(s)are chosen from cationic direct dyes or dyes commonly referred to as“basic” direct dyes or “basic dyes” on account of their affinity foracidic substances. The cationic dyes are preferentially chosen fromhydrazono, (poly)azo, polymethine such as styryl and (poly)arylmethanedyes. More preferentially, the cationic dye(s) of the invention arechosen from the hydrazono dyes of formulae (Va) and (V′a), the azo dyes(VIa) and (VI′a) and the diazo dyes (VIIa) below:

formulae (Va), (V′a), (VIa), (VI′a) and (VIIa) with:

-   -   Het⁺ representing a cationic heteroaryl radical, preferentially        bearing an endocyclic cationic charge, such as imidazolium,        indolium or pyridinium, optionally substituted, preferentially        with one or more (C₁-C₈) alkyl groups such as methyl;    -   Ar⁺ representing an aryl radical, such as phenyl or naphthyl,        bearing an exocyclic cationic charge, preferentially ammonium,        particularly tri(C₁-C₈)alkylammonium such as trimethylammonium;    -   Ar represents an aryl group, especially phenyl, which is        optionally substituted, preferentially with one or more        electron-donating groups such as i) optionally substituted        (C₁-C₈)alkyl, ii) optionally substituted (C₁-C₈)alkoxy, iii)        (di)(C₁-C₈)(alkyl)amino optionally substituted on the alkyl        group(s) with a hydroxyl group, iv) aryl(C₁-C₈)alkylamino, v)        optionally substituted N—(C₁-C₈)alkyl-N-aryl(C₁-C₈)alkylamino or        alternatively Ar represents a julolidine group;    -   Ar′ is an optionally substituted divalent (hetero)arylene group        such as phenylene, particularly para-phenylene, or naphthalene,        which are optionally substituted, preferentially with one or        more (C₁-C₈)alkyl, hydroxyl or (C₁-C₈)alkoxy groups;    -   Ar″ is an optionally substituted (hetero)aryl group such as        phenyl or pyrazolyl, which are optionally substituted,        preferentially with one or more groups (C₁-C₈)alkyl, hydroxyl,        (di)(C₁-C₈)(alkyl)amino, (C₁-C₈)alkoxy or phenyl;    -   R^(a) and R^(b), which may be identical or different, represent        a hydrogen atom or a (C₁-C₈)alkyl group, which is optionally        substituted, preferentially with a hydroxyl group;    -   or alternatively the substituent R^(a) with a substituent of        Het⁺ and/or R^(b) with a substituent of Ar and/or R^(a) with        R^(b) form, together with the atoms that bear them, a        (hetero)cycloalkyl;    -   particularly, R^(a) and R^(b) represent a hydrogen atom or a        (C₁-C₄)alkyl group, which is optionally substituted with a        hydroxyl group;    -   Q⁻ represents an anionic counterion as defined previously.

According to a preferred variant of the invention, the cationic dyes arechosen from the polymethine dyes of formulae (VIIIa) and (VIII′a) below:

formulae (VIIIa) or (VIII′a) with:

-   -   W⁺ representing a cationic heterocyclic or heteroaryl group,        particularly comprising a quaternary ammonium optionally        substituted with one or more (C₁-C₈)alkyl groups optionally        substituted especially with one or more hydroxyl groups;    -   W′⁺ representing a heterocyclic or heteroaryl radical as defined        for W+;    -   Ar representing a (hetero)aryl group such as phenyl or naphthyl,        optionally substituted preferentially with i) one or more        halogen atoms such as chlorine or fluorine; ii) one or more        (C₁-C₈)alkyl groups, preferably of C₁-C₄ such as methyl; iii)        one or more hydroxyl groups; iv) one or more (C₁-C₈)alkoxy        groups such as methoxy; v) one or more hydroxy(C₁-C₈)alkyl        groups such as hydroxyethyl, vi) one or more amino groups or        (di)(C₁-C₈)alkylamino, preferably with the C₁-C₄ alkyl part        optionally substituted with one or more hydroxyl groups, such as        (di)hydroxyethylamino, vii) with one or more acylamino        groups; viii) one or more heterocycloalkyl groups such as        piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as        pyrrolidinyl, pyridyl and imidazolinyl;    -   Ar′ is a (hetero)aryl radical as defined for Ar;    -   m′ represents an integer between 1 and 4 inclusive, and in        particular m has the value 1 or 2; more preferentially 1;    -   R^(c), R^(d), which may be identical or different, represent a        hydrogen atom or an optionally substituted (C₁-C₈)alkyl group,        preferentially of C₁-C₄, or alternatively R^(c) contiguous with        W⁺ or W′⁺ and/or R^(d) contiguous with Ar or Ar′ and/or        contiguous R^(c) and R^(d) form, with the atoms that bear them,        a (hetero)cycloalkyl, particularly R^(c) is contiguous with W⁺        or W′⁺ and forms a (hetero)cycloalkyl such as cyclohexyl;    -   Q⁻ as defined previously preferably represents a halide or a        mesylate.        Mention may be made more particularly of the azo and hydrazono        dyes bearing an endocyclic cationic charge of formulae (Va),        (V′a), (VIa) and (VI′a) as defined previously. More particularly        those of formulae (Va), (V′a) and (VIa) derived from the dyes        described in patent applications WO 95/15144, WO 95/01772 and        EP-714954. Preferentially, the cationic dyes comprise an        endocyclic cationic charge and have the following formula:

formulae (Va-1) and (Via-1) with:

-   -   R¹ representing a (C₁-C₄)alkyl group such as methyl;    -   R² and R³, which may be identical or different, represent a        hydrogen atom or a (C₁-C₄)alkyl group, such as methyl; and    -   R⁴ represents a hydrogen atom or an electron-donating group such        as optionally substituted (C₁-C₈)alkyl, optionally substituted        (C₁-C₈)alkoxy, or (di)(C₁-C₈)(alkyl)amino optionally substituted        on the alkyl group(s) with a hydroxyl group; particularly, R⁴ is        a hydrogen atom;    -   Z represents a CH group or a nitrogen atom, preferentially CH;    -   Q⁻ as defined previously preferably represents a halide or a        mesylate.    -   Particularly, the dyes of the invention are chosen from those of        formula (IIIa-1) and (IVa-1) is chosen from Basic Red 51, Basic        Yellow 87 and Basic Orange 31 or derivatives thereof:

with Q⁻ as defined previously preferably representing a halide or amesylate.

According to a particularly advantageous embodiment of the invention,the dye(s) are chosen from dyes of natural origin or “natural” dyes.

Among the natural dyes, mention may be made of lawsone, juglone, indigo,isatin, curcumin, chlorophyllin, laccaic acid, kermesic acid, carminicacid, sorghum, spinulosin, apigenidin, orceins, polyphenols orortho-diphenols (ODPs) and any extract rich in ODPs. Use may also bemade of extracts or decoctions comprising these natural dyes andespecially henna-based and/or indigo-based extracts or poultices.

According to a particularly preferred embodiment of the invention, thedye(s) are chosen from ortho-diphenol(s) or ODP(s).

The invention relates to one or more ODPs or mixtures of compoundscomprising one or more aromatic rings, at least one of which is abenzene ring substituted with at least two hydroxyl (OH) groups borne bytwo adjacent carbon atoms of said benzene group being present in thestructure of the ortho-diphenol(s).

The aromatic ring is more particularly a fused aryl or fusedheteroaromatic ring, i.e. optionally comprising one or more heteroatoms,such as benzene, naphthalene, tetrahydronaphthalene, indane, indene,anthracene, phenanthrene, indole, isoindole, indoline, isoindoline,benzofuran, dihydrobenzofuran, chroman, isochroman, chromene,isochromene, quinoline, tetrahydroquinoline and isoquinoline, saidaromatic ring comprising at least two hydroxyl groups borne by twoadjacent carbon atoms of the aromatic ring. Preferentially, the aromaticring of the ODPs according to the invention is a benzene ring.

The term “fused ring” means that at least two saturated or unsaturatedand heterocyclic or non-heterocyclic rings have a shared bond, i.e. atleast one ring is placed side-by-side with another ring.

The ODP(s) according to the invention may or may not be salified. Theymay also be in aglycone form (without bonded sugar) or in the form ofglycosylated compounds.

More particularly, the ODP(s) a) represent a compound of formula (II),or an oligomer, tautomer, optical isomer or geometrical isomer thereof,and also salts or solvates thereof, such as hydrates:

in which formula (II):

-   -   R¹ to R⁴, which may be identical or different, represent: i) a        hydrogen atom, ii) a halogen atom, or a group chosen from iii)        hydroxyl, iv) carboxyl, v) (C₁-C₂₀)alkyl carboxylate or        (C₁-C₂₀)alkoxycarbonyl, vi) optionally substituted amino, vii)        optionally substituted linear or branched (C₁-C₂₀)alkyl, viii)        optionally substituted linear or branched (C₂-C₂₀)alkenyl, ix)        optionally substituted cycloalkyl, x) (C₁-C₂₀)alkoxy, xi)        (C₁-C₂₀)alkoxy(C₁-C₂₀)alkyl, xii) (C₁-C₂₀)alkoxyaryl, xiii) aryl        which can optionally be substituted, xiv) aryl, xv) substituted        aryl, xvi) heterocyclic which is saturated or unsaturated,        optionally bearing a cationic or anionic charge and which is        optionally substituted and/or optionally fused with an aromatic        ring, preferably a benzene ring, said aromatic ring optionally        being substituted, in particular with one or more hydroxyl or        glycosyloxy groups, xvii) a radical containing one or more        silicon atoms;    -   or two of the substituents borne by two adjacent carbon atoms        R¹-R², R²-R³ or R³-R⁴ form, together with the carbon atoms        bearing them, a saturated or unsaturated and aromatic or        non-aromatic ring optionally containing one or more heteroatoms        and optionally fused with one or more saturated or unsaturated        rings optionally containing one or more heteroatoms. In        particular, the compound of formula (II) comprises from one to        four rings.

A particular embodiment of the invention relates to one or more ODPs offormula (II), two adjacent substituents R¹-R², R²-R³ or R³-R⁴ of whichcannot form, with the carbon atoms that bear them, a pyrrolyl radical.According to a variant, R² and R³ form a pyrrolyl or pyrrolidinylradical fused to the benzene ring bearing the two hydroxyls.

For the purposes of the present invention and unless otherwiseindicated:

-   -   the saturated or unsaturated and optionally fused rings may also        be optionally substituted;    -   the “alkyl” radicals are saturated, linear or branched,        generally C₁-C₂₀, particularly C₁-C₁₀, hydrocarbon-based        radicals, preferably C₁-C₆ alkyl radicals, such as methyl,        ethyl, propyl, butyl, pentyl and hexyl;    -   the “alkenyl” radicals are unsaturated and linear or branched        C₂-C₂₀ hydrocarbon-based radicals; preferably comprising at        least one double bond, such as ethylene, propylene, butylene,        pentylene, 2-methylpropylene and decylene;    -   the “aryl” radicals are monocyclic or fused or non-fused        polycyclic carbon-based radicals preferentially comprising from        6 to 30 carbon atoms, at least one ring of which is aromatic;        preferentially, the aryl radical is chosen from phenyl,        biphenyl, naphthyl, indenyl, anthracenyl and tetrahydronaphthyl;    -   the “alkoxy” radicals are alkyl-oxy radicals with alkyl as        defined previously, preferably C₁-C₁₀ alkyl, such as methoxy,        ethoxy, propoxy and butoxy;    -   the “alkoxyalkyl” radicals are (C₁-C₂₀)alkoxy(C₁-C₂₀)alkyl        radicals, such as methoxymethyl, ethoxymethyl, methoxyethyl,        ethoxyethyl, etc.;    -   the “cycloalkyl” radicals are C₄-C₈ cycloalkyl radicals,        preferably cyclopentyl and cyclohexyl radicals; the cycloalkyl        radicals may be substituted cycloalkyl radicals, in particular        substituted with alkyl, alkoxy, carboxylic acid, hydroxyl, amine        and ketone groups;    -   the “alkyl” or “alkenyl” radicals, when they are “optionally        substituted”, may be substituted with at least one atom or group        borne by at least one carbon atom chosen from: i) halogen; ii)        hydroxyl; iii) (C₁-C₂)alkoxy; iv) (C₁-C₁₀)alkoxycarbonyl; v)        (poly)hydroxy(C₂-C₄)alkoxy; vi) amino; vii) 5- or 6-membered        heterocycloalkyl; viii) optionally cationic 5- or 6-membered        heteroaryl, preferably imidazolium, optionally substituted with        a (C₁-C₄)alkyl radical, preferably methyl; ix) amino substituted        with one or two identical or different C₁-C₆ alkyl radicals        optionally bearing at least: a) one hydroxyl group, b) one amino        group optionally substituted with one or two optionally        substituted (C₁-C₃)alkyl radicals, it being possible for said        alkyl radicals to form, with the nitrogen atom to which they are        attached, a saturated or unsaturated and optionally substituted        5- to 7-membered heterocycle optionally comprising at least one        other nitrogen or non-nitrogen heteroatom, c) a quaternary        ammonium group —N⁺R′R″R′″, M⁻ for which R′, R″ and R′″, which        may be identical or different, represent a hydrogen atom or a        C₁-C₄ alkyl group; and M⁻ represents the counterion of the        corresponding organic acid, mineral acid or halide, d) or one        optionally cationic 5- or 6-membered heteroaryl radical,        preferentially imidazolium, optionally substituted with a        (C₁-C₄)alkyl radical, preferably methyl; x) acylamino        (—N(R)—C(O)—R′) in which the R radical is a hydrogen atom or a        (C₁-C₄)alkyl radical optionally bearing at least one hydroxyl        group and the R′ radical is a C₁-C₂ alkyl radical; a carbamoyl        ((R)₂N—C(O)—) radical in which the R radicals, which may be        identical or different, represent a hydrogen atom or a        (C₁-C₄)alkyl radical optionally bearing at least one hydroxyl        group; xi) alkylsulfonylamino (R′—S(O)₂—N(R)—) in which the R        radical represents a hydrogen atom or a (C₁-C₄)alkyl radical        optionally bearing at least one hydroxyl group and the R′        radical represents a (C₁-C₄)alkyl radical, a phenyl        radical; xii) aminosulfonyl ((R)₂N—S(O)₂—) in which the R        radicals, which may be identical or different, represent a        hydrogen atom or a (C₁-C₄)alkyl radical optionally bearing at        least one group chosen from a) hydroxyl, b) carboxyl —C(O)—OH in        the acid or salified form (preferably salified with an alkali        metal or a substituted or unsubstituted ammonium); xiii)        cyano; xiv) nitro; xv) carboxyl or glycosylcarbonyl; xvi)        phenylcarbonyloxy optionally substituted with one or more        hydroxyl groups; xvii) glycosyloxy; and phenyl group optionally        substituted with one or more hydroxyl groups;    -   the “aryl” or “heterocyclic” radicals or the aryl or        heterocyclic part of the radicals, when they are “optionally        substituted”, may be substituted with at least one atom or group        borne by at least one carbon atom chosen from:        -   i) (C₁-C₁₀)alkyl, preferably C₁-C₈ alkyl, optionally            substituted with one or more radicals chosen from the            following radicals: hydroxyl, (C₁-C₂)alkoxy,            (poly)hydroxy(C₂-C₄)alkoxy, acylamino, amino substituted            with two identical or different C₁-C₄ alkyl radicals            optionally bearing at least one hydroxyl group or it being            possible for the two radicals to form, with the nitrogen            atom to which they are attached, a saturated or unsaturated            and optionally substituted 5- to 7-membered, preferably 5-            or 6-membered, heterocycle optionally comprising another            nitrogen or non-nitrogen heteroatom; ii) halogen; iii)            hydroxyl; iv) C₁-C₂ alkoxy; v) C₁-C₁₀ alkoxycarbonyl; vi)            (poly)hydroxy(C₂-C₄)alkoxy; vii) amino; viii) 5- or            6-membered heterocycloalkyl; ix) optionally cationic 5- or            6-membered heteroaryl, preferably imidazolium, optionally            substituted with a (C₁-C₄)alkyl radical, preferably            methyl; x) amino substituted with one or two identical or            different C₁-C₆ alkyl radicals optionally bearing at            least: a) one hydroxyl group, b) one amino group optionally            substituted with one or two optionally substituted C₁-C₃            alkyl radicals, it being possible for said alkyl radicals to            form, with the nitrogen atom to which they are attached, a            saturated or unsaturated and optionally substituted 5- to            7-membered heterocycle optionally comprising at least one            other nitrogen or non-nitrogen heteroatom, c) one quaternary            ammonium group —N⁺R′R″R′″, M⁻ for which R′, R″ and R′″,            which may be identical or different, represent a hydrogen            atom or a C₁-C₄ alkyl group; and M⁻ represents the            counterion of the corresponding organic acid, mineral acid            or halide, d) one optionally cationic 5- or 6-membered            heteroaryl radical, preferably imidazolium, optionally            substituted with a (C₁-C₄)alkyl radical, preferably            methyl; xi) acylamino (—N(R)—C(O)—R′) in which the R radical            is a hydrogen atom or a C₁-C₄ alkyl radical optionally            bearing at least one hydroxyl group and the R′ radical is a            C₁-C₂ alkyl radical; xii) carbamoyl ((R)₂N—C(O)—) in which            the R radicals, which may be identical or different,            represent a hydrogen atom or a C₁-C₄ alkyl radical            optionally bearing at least one hydroxyl group; xiii)            alkylsulfonylamino (R′S(O)₂—N(R)—) in which the R radical            represents a hydrogen atom or a C₁-C₄ alkyl radical            optionally bearing at least one hydroxyl group and the R′            radical represents a C₁-C₄ alkyl radical, a phenyl            radical; xiv) aminosulfonyl ((R)₂N—S(O)₂—) in which the R            radicals, which may be identical or different, represent a            hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at            least one hydroxyl group; xv) carboxyl in the acid or            salified form (preferably salified with an alkali metal or a            substituted or unsubstituted ammonium); xvi) cyano; xvii)            nitro; xviii) polyhaloalkyl, preferably            trifluoromethyl; xix) a glycosylcarbonyl; xx) a            phenylcarbonyloxy group optionally substituted with one or            more hydroxyl groups; xxi) a glycosyloxy group; and xxii) a            phenyl group optionally substituted with one or more            hydroxyl groups;    -   for the purposes of the present invention, the term “glycosyl”        radical means a radical derived from a mono- or polysaccharide;    -   the radicals “containing one or more silicon atoms” are        preferably polydimethylsiloxane, polydiphenylsiloxane,        polydimethylphenylsiloxane or stearoxy dimethicone radicals;    -   the “heterocyclic” radicals are radicals comprising, in at least        one ring, one or more heteroatoms chosen in particular from O, N        and S, preferably O or N, optionally substituted in particular        with one or more alkyl, alkoxy, carboxyl, hydroxyl, amine or        ketone groups. These rings may comprise one or more oxo groups        on the carbon atoms of the heterocycle; mention may in        particular be made, among the heterocyclic radicals that may be        used, of furyl, pyranyl, pyrrolyl, imidazolyl, pyrazolyl,        pyridyl or thienyl groups; even more preferably, the        heterocyclic groups are fused groups, such as benzofuryl,        chromenyl, xanthenyl, indolyl, isoindolyl, quinolyl,        isoquinolyl, chromanyl, isochromanyl, indolinyl, isoindolinyl,        coumarinyl or isocoumarinyl groups, it being possible for these        groups to be substituted, in particular with one or more OH        groups.

The ODP(s) that are useful in the process of the invention may benatural or synthetic. Among the natural ODPs are compounds that may bepresent in nature and that are reproduced by chemical (semi)synthesis.

The salts of the ODPs of the invention may be salts of acids or ofbases. The acids may be mineral or organic. Preferably, the acid ishydrochloric acid, which results in chlorides.

The term “basifying agents” means that the bases as defined for e) maybe mineral or organic. In particular, the bases are alkali metalhydroxides, such as sodium hydroxide, which results in sodium salts.

According to a particular embodiment of the invention, the compositioncomprises, as ingredient a), one or more synthetic ODPs that do notexist in nature.

According to another preferred embodiment of the invention, thecomposition that is useful in the process for dyeing keratin fibrescomprises, as ingredient a), one or more natural ODPs.

More particularly, the ODP(s) that may be used in the process of theinvention according to a) are in particular:

-   -   flavanols, for instance catechin and epicatechin gallate,    -   flavonols, for instance quercetin,    -   anthocyanidins, for instance cyanidin, delphinidin and        petunidin,    -   anthocyanins or anthocyans, for instance myrtillin,    -   ortho-hydroxybenzoates, for example gallic acid salts,    -   flavones, for instance luteolin,    -   hydroxystilbenes, for example 3,3′,4,5′-tetrahydroxystilbene,        optionally oxylated (for example glucosylated),    -   3,4-dihydroxyphenylalanine and derivatives thereof,    -   2,3-dihydroxyphenylalanine and derivatives thereof,    -   4,5-dihydroxyphenylalanine and derivatives thereof,    -   dihydroxycinnamates, such as caffeic acid and chlorogenic acid,    -   ortho-polyhydroxycoumarins,    -   ortho-polyhydroxyisocoumarins,    -   ortho-polyhydroxycoumarones,    -   ortho-polyhydroxyisocoumarones,    -   ortho-polyhydroxychalcones,    -   ortho-polyhydroxychromones,    -   quinones,    -   hydroxyxanthones,    -   1,2-dihydroxybenzene and derivatives thereof,    -   1,2,4-trihydroxybenzene and derivatives thereof,    -   1,2,3-trihydroxybenzene and derivatives thereof,    -   2,4,5-trihydroxytoluene and derivatives thereof,    -   proanthocyanidins and especially the proanthocyanidins A1, A2,        B1, B2, B3 and C1,    -   chroman and chromene compounds,    -   proathocyanins,    -   tannic acid,    -   ellagic acid,    -   and mixtures of the preceding compounds.

According to the invention, the term “chromene or chroman” ODP compoundsmeans ODPs which comprise, in their structure, at least one bicycle offormula (A) below:

the endocyclic bond

representing a carbon-carbon single bond or else a carbon-carbon doublebond, as illustrated by formula (A1) below, denoting the chromenefamily, and formula (A2) below, denoting the chroman family:

More particularly, the ODPs of the invention are of formula (A) and arepreferably chosen from the dyes of the following formulae:

-   -   formula (III), comprising, in its structure, the bicycle of        formula (A2):

and also the tautomeric and/or mesomeric forms thereof, thestereoisomers thereof, the addition salts thereof with a cosmeticallyacceptable acid or base, and the hydrates thereof;in which formula (III):

-   -   represents a carbon-carbon single bond or a carbon-carbon double        bond, the sequence of these        bonds denoting two carbon-carbon single bonds and two        carbon-carbon double bonds, said bonds being conjugated,    -   X represents a group:

-   -   R¹, R², R³, R⁴, R⁵ and R⁶, which may be identical or different,        represent a hydrogen atom, a hydroxyl group, an optionally        substituted alkyl group, an optionally substituted alkoxy group        or an optionally substituted acyloxy group; and    -   formula (IV), comprising, in its structure, the bicycle of        formula (A1):

and also the tautomeric and/or mesomeric forms thereof, thestereoisomers thereof, the addition salts thereof with a cosmeticallyacceptable acid or base, and the hydrates thereof;in which formula (IV):

-   -   R₁₁, R₁₂, R₁₃, R₁₆, R₁₉ and R₂₀, which may be identical or        different, represent a hydrogen atom or a C₁-C₄ alkyl radical,        and    -   R₁₄, R₁₅, R₁₇ and R₁₈, which may be identical or different,        represent a hydrogen atom, a hydroxyl radical or a C₁-C₄ alkoxy        radical.

As regards the ortho-diphenols of formula (III) as defined above, theymay be found in two tautomeric forms denoted (IIIa) and (IIIb):

The alkyl radicals mentioned in the preceding definitions of thesubstituents are saturated and linear or branched hydrocarbon-basedradicals, generally C₁-C₂₀, particularly C₁-C₁₀, preferably C₁-C₆,hydrocarbon-based radicals, such as methyl, ethyl, propyl, butyl, pentyland hexyl.

The alkoxy radicals are alkyl-oxy radicals with the alkyl radicals asdefined above and preferably the alkoxy radicals are C₁-C₁₀ alkoxyradicals, such as methoxy, ethoxy, propoxy and butoxy.

The alkyl or alkoxy radicals, when they are substituted, may besubstituted with at least one substituent borne by at least one carbonatom chosen from: i) a halogen atom or ii) a hydroxyl group; iii) aC₁-C₂ alkoxy group; iv) a C₁-C₁₀ alkoxycarbonyl group; v) a(poly)hydroxy(C₂-C₄)alkoxy group; vi) an amino group; vii) a 5- or6-membered heterocycloalkyl group; viii) an optionally cationic 5- or6-membered heteroaryl group, preferably imidazolium, optionallysubstituted with a (C₁-C₄)alkyl radical, preferably methyl; ix) an aminoradical substituted with one or two identical or different C₁-C₆ alkylradicals optionally bearing at least: a) one hydroxyl group,

b) one amino group optionally substituted with one or two optionallysubstituted C₁-C₃ alkyl radicals, it being possible for said alkylradicals to form, with the nitrogen atom to which they are attached, asaturated or unsaturated and optionally substituted 5- to 7-memberedheterocycle optionally comprising at least one other nitrogen ornon-nitrogen heteroatom, c) one quaternary ammonium group —N⁺R′R″R′″, M⁻for which R″, R″ and R′″, which may be identical or different, representa hydrogen atom or a C₁-C₄ alkyl group and M⁻ represents the counterionof the corresponding organic acid, mineral acid or halide, d) or oneoptionally cationic 5- or 6-membered heteroaryl radical, preferablyimidazolium, optionally substituted with a (C₁-C₄)alkyl radical,preferably methyl; x) an acylamino (—NR—COR′) radical in which the Rradical is a hydrogen atom or a C₁-C₄ alkyl radical optionally bearingat least one hydroxyl group and the R′ radical is a C₁-C₂ alkyl radical;xi) a carbamoyl ((R)₂N—CO—) radical in which the R radicals, which maybe identical or different, represent a hydrogen atom or a C₁-C₄ alkylradical optionally bearing at least one hydroxyl group; xii) analkylsulfonylamino (R′SO₂—NR—) radical in which the R radical representsa hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at least onehydroxyl group and the R′ radical represents a C₁-C₄ alkyl radical, aphenyl radical; xiii) an aminosulfonyl ((R)₂N—SO₂—) radical in which theR radicals, which may be identical or different, represent a hydrogenatom or a C₁-C₄ alkyl radical optionally bearing at least one hydroxylgroup; xiv) a carboxyl radical in the acid or salified form (preferablysalified with an alkali metal or a substituted or unsubstitutedammonium); xv) a cyano group; xvi) a nitro group; xvii) a carboxyl orglycosylcarbonyl group; xviii) a phenylcarbonyloxy group optionallysubstituted with one or more hydroxyl groups; xix) a glycosyloxy group;and xx) a phenyl group optionally substituted with one or more hydroxylgroups.

The term “glycosyl radical” means a radical derived from amonosaccharide or polysaccharide.

Preferably, the alkyl or alkoxy radicals of formula (III) areunsubstituted.

According to a particular embodiment of the invention, the dyes offormula (III) comprise a radical R₆ representing a hydroxyl group.

Another particular embodiment of the invention relates to the ODPs offormula (III) for which the radical R₁ represents a hydrogen atom or ahydroxyl group.

More particularly, the composition according to the invention maycomprise one or more ODPs of formula (III) chosen from haematoxylin,haematein, brazilin and brazilein.

Brazilein is a conjugated form of a chroman compound of formula (A2).The tautomeric structures (IIIa) and (IIIb) illustrated above are foundin the scheme below.

Among the ODPs of haematoxylin/haematein and brazilin/brazilein type,examples that may be mentioned include haematoxylin (Natural Black 1according to the INCI name) and brazilin (Natural Red 24 according tothe INCI name), dyes of the indochroman family, which are commerciallyavailable. The latter dyes may exist in an oxidized form and may beobtained synthetically or by extraction of plants or vegetables known tobe rich in these dyes.

The ODPs of formula (III) may be used in the form of extracts. Use maybe made of the following plant extracts (genus and species):Haematoxylon campechianum, Haematoxylon brasiletto, Caesalpiniaechinata, Caesalpinia sappan, Caesalpinia spinosa and Caesalpiniabrasiliensis.

The extracts are obtained by extracting the various plant parts, forinstance the root, the wood, the bark or the leaves.

According to one particular embodiment of the invention, the naturalODPs are of formula (I) and are obtained from logwood, pernambuco wood,sappan wood and Brazil wood.

According to a particular embodiment of the invention, the ODPs are offormula (IV), preferably those for which R₁₁ and R₁₃ represent an alkylradical, preferably methyl.

Preferably, R₁₂, R₁₆, R₁₉ and R₂₀ denote, independently of each other, ahydrogen atom or an alkyl radical, preferably methyl.

Preferably, R₁₄ and R₁₇ denote, independently of each other, a hydrogenatom or an alkoxy radical, preferably methoxy.

Preferably, R₁₈ and R₁₅ denote, independently of each other, a hydrogenatom, a hydroxyl radical or an alkoxy radical, preferably methoxy.

A first particularly preferred family of ODPs that are suitable for usein the present invention is that of the dyes corresponding to formula(II) above for which R₁₂, R₁₅, R₁₆, R₁₇, R₁₉ and R₂₀ each represent ahydrogen atom. R₁₁ and R₁₃ each represent a methyl radical and R₁₄represents a methoxy radical.

The preferred ODPs of this first family include those for which R₁₈represents a methoxy radical (santalin B) or a hydroxyl radical(santalin A).

A second particularly preferred family of ODPs that are suitable for usein the present invention is that of the dyes corresponding to theformula (IV) above for which:

-   -   R₁₁ and R₁₃ each represent a methyl radical,    -   R₁₇ represents a methoxy radical.

A preferred dye of this second family is that for which, in addition,R₁₉ represents a methyl radical, R₂₀, R₁₂, R₁₄, R₁₈ and R₁₆ eachrepresent a hydrogen atom and R₁₅ represents a hydroxyl radical(santarubin A).

A second preferred dye of this second family is that for which R₁₈, R₂₀,R₁₂, R₁₄ and R₁₆ represent a hydrogen atom, R₁₅ represents a methoxyradical and R₁₉ represent a methyl radical (santarubin B).

A third preferred family of ODPs of this second family is that for whichR₂₀, R₁₂, R₁₄, R₁₅, R₁₆ and R₁₉ represent hydrogen and R₁₈ represents ahydroxyl radical (santarubin C).

The preferred ODP(s) of this second family is that for which R₁₅represents a methoxy radical, R₁₈ and R₁₄ represent a hydrogen atom andR₂₀, R₁₂, R₁₆ and R₁₉ represent a methyl radical(tetra-O-methylsantarubin).

The ODP(s) of formula (IV) may be used in the form of extracts. Use maybe made of plant extracts of red woods, bringing together generally thespecies of red woods from Asia and West Africa of the genus Pterocarpusand of the genus Baphia. These woods are, for example, Pterocarpussantalinus, Pterocarpus osun, Pterocarpus soyauxii, Pterocarpuserinaceus, Pterocarpus indicus or Baphia nitida. These woods may also becalled padauk, sandalwood, narra wood, camwood or bar wood.

Thus, extracts that may be used, comprising ODPs of formula (II), in thepresent invention may be obtained, for example, from red sandalwood(Pterocarpus santalinus) by aqueous basic extraction, such as theproduct sold under the trade name Santal Concentre SL 709C by thecompany COPIAA, or also by means of solvent extraction of sandalwoodpowder, such as the product sold under the trade name Santal Poudre SLPP by the same company COPIAA. Mention may also be made of theaqueous/alcoholic extract of powdered red sandalwood from the companyAlban Muller.

Extracts also suitable for the present invention can be obtained fromwoods such as camwood (Baphia nitida) or also bar wood (Pterocarpussoyauxii, Pterocarpus erinaceus): the latter is thus split up and thenground: a conventional alcoholic extraction or one by percolation issubsequently carried out on this ground material in order to collect apulverulent extract particularly suitable for the implementation of thepresent invention.

The ODP salts of formulae (III) and (IV) of the invention may be saltsof acids or bases that are cosmetically acceptable.

The acids may be mineral or organic. Preferably, the acid ishydrochloric acid, which results in chlorides.

The bases may be mineral or organic. In particular, the bases are alkalimetal hydroxides such as sodium hydroxide which leads to sodium salts.

Preferably, the ODP(s) of formulae (III) and (IV) included in thecomposition according to the invention result from plant extracts. Usemay also be made of mixtures of plant extracts.

The natural extracts of ODPs according to the invention may be in theform of powders or liquids. Preferably, the extracts are in powder form.

In particular, the ODPs of the invention are included among catechin,quercetin, brazilin, haematein, haematoxylin, chlorogenic acid, caffeicacid, gallic acid, catechol, L-DOPA, pelargonidin, cyanidin,(−)-epicatechin, (−)-epigallocatechin, (−)-epigallocatechin 3-gallate(EGCG), (+)-catechin, isoquercetin, pomiferin, esculetin,6,7-dihydroxy-3-(3-hydroxy-2,4-dimethoxyphenyl)coumarin, santalin AC,mangiferin, butein, maritimetin, sulfuretin, robtein, betanidin,pericampylinone A, theaflavin, proanthocyanidin A2, proanthocyanidin B2,proanthocyanidin C1, procyanidins DP 4-8, tannic acid, purpurogallin,5,6-dihydroxy-2-methyl-1,4-naphthoquinone, alizarin, wedelolactone,variegatic acid, gomphidic acid, xerocomic acid and carnosol, andnatural extracts containing them.

Preferably, the ODPs of the invention are chromenes or chromans and arechosen from haematein, haematoxylin, brazilein, brazilin and santalin A.

The term “carboxylate” means carboxylic acid salt.

When the dye precursors have D and L forms, the two forms may be used inthe compositions according to the invention, as may the racemicmixtures.

According to one embodiment, the natural ODPs are derived from extractsof animals, bacteria, fungi, algae, plants and fruits, used in theirentirety or partially. In particular regarding plants, the extracts arederived from fruit, including citrus fruit, from vegetables, from treesand from shrubs. Use may also be made of mixtures of these extracts,which are rich in ODPs as defined above.

Preferably, the natural ODP(s) of the invention are derived fromextracts of plants or plant parts.

For the purposes of the invention, these extracts will be placed in thesame category as compounds a).

The extracts are obtained by extraction of various plant parts, forinstance the root, the wood, the bark, the leaf, the flower, the fruit,the seed, the pod or the peel.

Among the plant extracts, mention may be made of extracts of tea leavesand of rose.

Among the fruit extracts, mention may be made of extracts of apple, ofgrape (in particular of grape seed) or extracts of cocoa beans and/orpods.

Among the vegetable extracts, mention may be made of extracts of potatoor of onion peel.

Among the extracts of tree wood, mention may be made of extracts of pinebark and extracts of logwood.

Use may also be made of mixtures of plant extracts.

According to a particular embodiment of the invention, theortho-diphenol derivative(s) are natural extracts, rich in ODPs.

According to a preferred embodiment, the dye(s) of the invention aresolely natural extracts.

Preferentially, the dye(s) according to the invention are chosen fromcatechin, quercetin, haematein, haematoxylin, brazilin, brazilein,gallic acid and tannic acid, and natural extracts containing them chosenfrom grape marc, pine bark, green tea, onion, cocoa bean, logwood, redwood and gall nut.

More preferentially, the ODP(s) of the invention are chosen from:

-   -   haematein, brazilein, gallic acid or tannic acid, when the        dyeing process does not use a chemical oxidizing agent;    -   or else    -   haematoxylin, brazilin, gallic acid or tannic acid, when the        dyeing process uses a chemical oxidizing agent.

The natural extracts according to the invention may be in the form ofpowders or liquids. Preferably, the extracts of the invention areprovided in the form of powders.

According to the invention, the synthetic or natural dye(s) and/or thenatural extract(s) used as ingredient a) in one or more cosmeticcompositions that are useful in the process according to the inventionpreferably represent from 0.001% to 20% by weight of the total weight ofthe composition(s) containing them.

As regards the pure dyes, especially the pure ODPs, the content in thecomposition(s) containing them is preferably between 0.001% and 5% byweight of each of these compositions containing them.

As regards the extracts, the content in the composition(s) containingthe extracts per se is preferably between 0.1% and 20% by weight of eachof these compositions, and better still between 0.5% and 10% by weightof the compositions containing them.

b) Titanium Salt(s):

The titanium salt(s) of the invention may be one or more organic ormineral titanium salts.

For the purposes of the present invention, the term “organic titaniumsalt” means the salts per se resulting from the action of at least oneorganic acid on Ti.

The term “organic acid” means an acid, i.e. a compound that is capableof releasing a cation or proton H⁺ or H₃O⁺, in aqueous medium, whichcomprises at least one optionally unsaturated, linear or branched C₁-C₂₀hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl groupand at least one acid chemical function chosen in particular fromcarboxyl COOH, sulfuric SO₃H, SO₂H, and phosphoric PO₃H₂, PO₄H₂. Inparticular, the organic acid(s) for forming the organic titanium salt(s)of the invention are chosen from the carboxylic acid(s) of formula (I)as defined previously and are preferably α-hydroxy acids such as lacticacid, glycolic acid, tartaric acid or citric acid.

Preferentially, the organic titanium salt derived from the action of oneor more organic acids as defined previously, preferably carboxylic acidsof formula (I) as defined previously, is an optionally charged (inparticular negatively charged) complex, which is complexed with one ormore carboxylate groups of carboxylic acids.

Preferentially, the organic titanium salt(s) of the invention are chosenfrom those of formula (I-A) below:

in which formula (I-A):

-   -   A is identical to that of formula (I);    -   n, n′ and n″, which may be identical or different, are equal to        1, 2, 3 or 4 and n′+n″=6;    -   M₁ and M₂, which may be identical or different, represent a        cationic counterion chosen in particular from cations of an        alkali metal such as Na or K or of an alkaline-earth metal such        as Ca or an organic cation such as ammonium, preferably ammonium        or a hydrogen atom;    -   TiY_(n″) denoting Ti(OH)_(n″), or Ti(O)_(n″/2), or        Ti(OH)_(m1)(O)_(m2) with m₁+m₂=n″.

Preferentially, the radical A of compound (I-A) as defined previouslyrepresents a monovalent (C₁-C₆)alkyl or polyvalent (C₁-C₆)alkylene groupoptionally substituted with one or more hydroxyl groups, and nrepresenting an integer between 0 and 5, such as between 0 and 2,inclusive; in particular, the carboxylic acid(s) used to form theorganic titanium salt(s) of the invention are chosen from α-hydroxyacids; preferably, the acid is chosen from citric acid, lactic acid,tartaric acid and glycolic acid, better still from lactic acid andglycolic acid.

Preferentially, the organic titanium salt(s) of the invention are chosenfrom those of formula (I-B) below:

in which formula (I-B):

-   -   L′ and L″, which may be identical or different, represent a        divalent (hetero)arylene, (C₁-C₆)alkylene or (C₂-C₆)alkenylene        group, said alkylene and arylene groups being optionally        substituted with one or more atoms or groups chosen from halo,        (C₁-C₄)alkyl, hydroxyl, thiol and (di)(C₁-C₄)(alkyl)amino,        carboxyl, and/or optionally interrupted with one or more        heteroatoms such as oxygen;    -   preferably, L′ and L″ are identical and represent a methylene or        ethylene group optionally substituted with a (C₁-C₄)alkyl group;    -   X′ and X″, which may be identical or different, represent a        heteroatom such as oxygen, sulfur or amino R^(c)—N with R^(c)        representing a hydrogen atom or a (C₁-C₄)alkyl group;        preferably, X′ and X″ are identical and represent an oxygen        atom;    -   Y and Y′, which may be identical or different, are as defined        for X′ and X″; preferably, Y and Y′ are identical and represent        an oxygen atom;    -   R^(a) and R^(b), which may be identical or different, represent        a hydrogen atom or a (C₁-C₆)alkyl, (C₂-C₆)alkenyl or        (hetero)aryl group; particularly, R^(a) and R^(b), which are        identical, represent a hydrogen atom or a (C₁-C₄)alkyl group,        preferably hydrogen;    -   M⁺, which may be identical or different, represents a cationic        counterion such as a cation of an alkali metal (Na or K) or of        an alkaline-earth metal (Ca) or an organic cation such as        ammonium, preferably ammonium.

Preferably, the organic titanium salt(s) of the dyeing process aredihydroxybis(lactato)titanium(IV) salts such as those having thefollowing formula:

The dyeing process may use one or more organic acids b1) of formula (I)as defined previously.

According to an advantageous variant, the dyeing process also uses b1)one or more carboxylic acids of formula (I) as defined previously. Morepreferentially, the carboxylic acid(s) b1) are other than the carboxylicacids complexed to the Ti salts.

For example, if the carboxylic acid complexed to the titanium salt b) islactic acid or the carboxylate salt thereof (lactate), the second acidb1) is other than lactic acid or lactate, and may be, for example,glycolic acid.

For the purposes of the present invention, the term “mineral titaniumsalt” means the salts per se derived from the action of a mineral acidon Ti.

The term “mineral acid” means an acid which does not comprise carbonatoms, apart from carbonic acid.

The mineral titanium salts are preferably chosen from titanium halides,titanium sulfates and titanium phosphates. Preferably, the titaniumsalts are mineral Ti(II), Ti(III) or Ti(IV) salts, more particularlyTi(III) or Ti(IV).

Preferably, the titanium salt(s) are organic titanium salts, and betterstill organic Ti(IV) salts. According to an advantageous embodiment ofthe invention, the organic Ti salt consists of a Ti(IV) atom and of 2 to3 molar equivalents of at least one carboxylic acid of formula (I).

The titanium salt(s) (b) are present in the cosmetic composition(s) usedin the process according to the invention in a content ranging from0.001% to 20% by weight, relative to the total weight of thecomposition(s) containing them.

Particularly, the organic titanium salt(s) and the mineral titaniumsalt(s) according to the invention are soluble in water in a proportionof at least 0.0001 g/I and better still at least 1 g/l.

c) Cellulose-Based Polysaccharide(s)

In accordance with the present invention, the dyeing process uses c) oneor more cellulose-based polysaccharides, i.e. one or morecellulose-based polysaccharide polymers, which are preferablythickeners.

The cellulose-based polymers may be associative or non-associativeanionic, cationic, amphoteric or nonionic polymers.

According to the invention, the term “cellulose-based polysaccharide”means any polymer bearing in its structure sequences of glucose residueslinked via β-1,4 bonds; besides unsubstituted celluloses, the cellulosederivatives may be anionic, cationic, amphoteric or nonionic. Thus, thecellulose-based polysaccharides of the invention may be chosen fromunsubstituted celluloses, including those in a microcrystalline form,and cellulose ethers. Among these cellulose-based polysaccharides,cellulose ethers, cellulose esters and cellulose ester ethers aredistinguished. Among the cellulose esters are mineral esters ofcellulose (cellulose nitrates, sulfates, phosphates, etc.), organiccellulose esters (cellulose monoacetates, triacetates, amidopropionates,acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.),and mixed organic/mineral esters of cellulose, such as celluloseacetatebutyrate sulfates and cellulose acetatepropionate sulfates. Amongthe cellulose ester ethers, mention may be made ofhydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

The term “associative polymers” means polymers that are capable, in anaqueous medium, of reversibly combining with each other or with othermolecules. Their chemical structure more particularly comprises at leastone hydrophilic region and at least one hydrophobic region, preferablyone or more hydrophobic hydrocarbon-based side chains.

The term “hydrophobic group” means a radical or polymer with a saturatedor unsaturated, linear or branched hydrocarbon-based chain, comprisingat least 10 carbon atoms, preferably from 10 to 30 carbon atoms, inparticular from 12 to 30 carbon atoms and more preferentially from 18 to30 carbon atoms. Preferentially, the hydrocarbon-based group is derivedfrom a monofunctional compound. By way of example, the hydrophobic groupmay be derived from a fatty alcohol such as stearyl alcohol, dodecylalcohol or decyl alcohol. It may also denote a hydrocarbon-basedpolymer, for instance polybutadiene. According to a particularembodiment of the invention, the cellulose-based polysaccharide(s) arenon-associative.

The “non-associative” cellulose-based polysaccharides of the inventionare cellulose-based polysaccharides not comprising any fatty chains,i.e. preferably not comprising any C₁₀-C₃₀ chains in their structure.

According to a first variant, the non-associative cellulose-basedpolysaccharide(s) are nonionic. Mention may be made of nonioniccellulose ethers without a C₁₀-C₃₀ fatty chain, i.e. which are“non-associative”, mention may be made of (C₁-C₄)alkylcelluloses, suchas methylcelluloses and ethylcelluloses (for example, Ethocel standard100 Premium from Dow Chemical); (poly)hydroxy(C₁-C₄)alkylcelluloses,such as hydroxymethylcelluloses, hydroxyethylcelluloses (for example,Natrosol 250 HHR provided by Aqualon) and hydroxypropylcelluloses (forexample, Klucel EF from Aqualon); mixed(poly)hydroxy(C₁-C₄)alkyl(C₁-C₄)alkylcelluloses, such ashydroxypropylmethylcelluloses (for example, Methocel E4M from DowChemical), hydroxyethylmethylcelluloses, hydroxyethylethylcelluloses(for example, Bermocoll E 481 FQ from Akzo Nobel) andhydroxybutylmethylcelluloses.

According to a second variant, the non-associative cellulose-basedpolysaccharide(s) are anionic. Among the anionic cellulose etherswithout a fatty chain, mention may be made of(poly)carboxy(C₁-C₄)alkylcelluloses and salts thereof. Examples that maybe mentioned include carboxymethylcelluloses,carboxymethylmethylcelluloses (for example Blanose 7M from the companyAqualon) and carboxymethylhydroxyethylcelluloses, and the sodium saltsthereof.

According to a third variant, the non-associative cellulose-basedpolysaccharide(s) are cationic. Among the cationic cellulose etherswithout a fatty chain, mention may be made of cationic cellulosederivatives such as cellulose copolymers or cellulose derivativesgrafted with a water-soluble quaternary ammonium monomer, and describedin particular in patent U.S. Pat. No. 4,131,576, such as(poly)hydroxy(C₁-C₄)alkyl celluloses, for instance hydroxymethyl-,hydroxyethyl- or hydroxypropylcellu loses grafted especially with amethacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.The commercial products corresponding to this definition are moreparticularly the products sold under the names Celquat® L 200 andCelquat® H 100 by the company National Starch.

According to another particular embodiment of the invention, thecellulose-based polysaccharide(s) are associative.

Mention may be made especially of quaternized(poly)hydroxyethylcelluloses modified with groups comprising at leastone fatty chain, such as alkyl, arylalkyl or alkylaryl groups comprisingat least 8 carbon atoms, or mixtures thereof. The alkyl radicals borneby the above quaternized celluloses or hydroxyethylcelluloses preferablycomprise from 8 to 30 carbon atoms. The aryl radicals preferably denotephenyl, benzyl, naphthyl or anthryl groups. Examples of quaternizedalkylhydroxyethylcelluloses containing C₈-C₃₀ fatty chains that may beindicated include the products Quatrisoft LM 200®, Quatrisoft LM-X529-18-A®, Quatrisoft LM-X 529-18B® (C₁₂ alkyl) and Quatrisoft LM-X529-8® (C₁₈ alkyl) sold by the company Aqualon, and the productsCrodacel QM®, Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (C₁₈ alkyl) soldby the company Croda and the product Softcat SL 100® sold by the companyAqualon.

Mention may also be made of celluloses or derivatives thereof, modifiedwith groups comprising at least one fatty chain, such as alkyl,arylalkyl or alkylaryl groups or mixtures thereof in which the alkylgroups are of C₈, and in particular:

-   -   nonionic alkylhydroxyethylcelluloses such as the products        Natrosol Plus Grade 330 CS and Polysurf 67 (C₁₆ alkyl) sold by        the company Aqualon;    -   nonionic nonoxynylhydroxyethylcelluloses such as the product        Amercell HM-1500 sold by the company Amerchol;    -   nonionic alkylcelluloses such as the product Bermocoll EHM 100        sold by the company Berol Nobel.

Among the cellulose-based polysaccharides according to the invention,mention may be made of fatty-phase thickeners, especially polymersbearing in the backbone at least one crystallizable block. Ascellulose-based polysaccharides, which are in particular fatty-phasethickeners, use may thus be made of semicrystalline cellulose-basedpolysaccharides. The semicrystalline cellulose-based polysaccharidesthat may be used in the context of the invention may be non-crosslinkedor partially crosslinked, provided that the degree of crosslinking doesnot impede their dissolution or dispersion in the liquid oily phase byheating above their melting point. It may then be a case of chemicalcrosslinking, by reaction with a multifunctional monomer during thepolymerization. It may also be a case of physical crosslinking, whichmay then be due either to the establishment of bonds of hydrogen ordipolar type between groups borne by the polysaccharide, for instancedipolar interactions between carboxylate ionomers, these interactionsbeing in small amount and borne by the polymer backbone; or due to aphase separation between the crystallizable blocks and the amorphousblocks borne by the polysaccharide.

Preferably, the semicrystalline cellulose-based polysaccharides that aresuitable for use in the invention are non-crosslinked.

According to a particular embodiment of the invention, thecellulose-based polysaccharide(s) are especially monoalkyl or polyalkylesters of cellulose and of fatty acids, especially corresponding toformula (C1) below:

in which formula (C1):

-   -   n is an integer ranging from 3 to 200, especially ranging from        20 to 150 and in particular ranging from 25 to 50,    -   R₁, R₂ and R₃, which may be identical or different, are chosen        from hydrogen and an acyl group (R—C(O)—) in which the radical R        is a linear or branched, saturated or unsaturated        hydrocarbon-based group containing from 7 to 29, in particular        from 7 to 21, especially from 11 to 19, more particularly from        13 to 17, or even 15, carbon atoms, with the proviso that at        least one of said radicals R₁, R₂ or R₃ is other than hydrogen.

In particular, R₁, R₂ and R₃ may represent hydrogen or an acyl group(R—C(O)—) in which R is a hydrocarbon-based radical as defined above,with the proviso that at least two of said radicals R₁, R₂ and R₃ areidentical and other than hydrogen.

The radicals R₁, R₂ and R₃ may all contain an acyl group (R—C(O)), whichis identical or different and especially identical.

In particular, n mentioned previously advantageously ranges from 25 to50 and is especially equal to 38 in the general formula of thesaccharide ester that may be used in the present invention.

In particular, when the radicals R₁, R₂ and/or R₃, which may beidentical or different, contain an acyl group (R—C(O)), these radicalsmay be chosen especially from caprylic, capric, lauric, myristic,palmitic, stearic, arachic, behenic, isobutyric, isovaleric,2-ethylbutyric, ethylmethylacetic, isoheptanoic, 2-ethylhexanoic,isononanoic, isodecanoic, isotridecanoic, isomyristic, isopalmitic,isostearic, isoarachic, isohexanoic, decenoic, dodecenoic,tetradecenoic, myristoleic, hexadecenoic, palmitoleic, oleic, elaidic,asclepinic, gondoleic, eicosenoic, sorbic, linoleic, linolenic, punicic,stearidonic, arachidonic and stearolic radicals, and mixtures thereof.

The cellulose-based polysaccharides, which are in particular thickeners,may be used alone or as mixtures in all proportions. Preferably, thethickeners are aqueous-phase thickeners.

Preferably, the cellulose-based polysaccharides in accordance with thepresent invention advantageously have in solution or in dispersion, at1% active material in water, a viscosity, measured using a rheometer at25° C., of greater than 0.1 ps and even more advantageously greater than0.2 cp, at a shear rate of 200 s⁻¹.

Preferably, the cellulose-based polysaccharide(s) c) of the inventionare chosen from cellulose ethers, in particular hydroxyalkylcelluloses,in particular hydroxy(C₁-C₄)alkylcelluloses, and especially chosen fromhydroxymethylcelluloses, hyd roxyethylcellu loses andhydroxypropylcelluloses.

The hydroxyalkylcelluloses may be nonionic, cationic and anionic. Theyare preferably nonionic. The hydroxyalkylcelluloses of the invention arepreferably hydroxyethylcelluloses and more preferentially nonionichydroxyethylcelluloses.

Use will be made even more preferentially of nonionichydroxyethylcelluloses free of fatty chains or ofcetylhydroxyethylcelluloses, for instance the compounds sold under thenames Polysurf 67CS®, Natrosol 250MR®, Natrosol 250HHR® and NatrosolPlus 330® by the company Ashland, and mixtures thereof.

The cellulose-based polysaccharide(s) of the invention may be present inthe dye composition(s) of the invention in contents ranging from 0.01%to 30% by weight, in particular from 0.05% to 20% by weight and betterstill from 0.1% to 10% by weight, relative to the total weight of thecomposition containing them.

d) Liquid Organic Compound(s) with a Value δH<16 (MPa)^(1/2)

According to a particular preferred embodiment of the invention, thedyeing process also uses d) one or more liquid organic compounds whichhave a Hansen solubility parameter value δH of less than 16 (MPa)^(1/2)at 25° C. and preferably less than or equal to 15 (MPa)^(1/2).

It is understood that the liquid organic compound(s) with a Hansensolubility parameter value δH of less than 16 (MPa)^(1/2) at 25° C. d)are different from the carboxylic acid(s) b1) of formula (I) as definedpreviously. It is also understood that the organic compound(s) with asolubility parameter value δH<16 (MPa)^(1/2) at 25° C. d) are soluble inwater with a solubility of greater than 10 g/l of water at 25° C.

For the purposes of the present invention, the term “liquid organiccompound” means an organic compound that is liquid at room temperatureat 25° C.

The liquid organic compound(s) with a Hansen solubility parameter valueδH of less than 16 (MPa)^(1/2) at 25° C. are described, for example, inthe reference book Hansen solubility parameters A user's handbook,Charles M. Hansen, CRC Press, 2000, pages 167 to 185 and also in thebook Handbook of solubility parameters and other cohesion parameters CRCPress, pages 95 to 121 and pages 177 to 185, The 3 dimensionalsolubility parameter & solvent diffusion coefficient, their importancein surface coating formulation, Charles M. Hansen, Copenhagen DanishTechnical Press, 1967, pages 13-29.

As a reminder, the organic compounds have a global Hansen solubilityparameter δ, which is defined in the article “Solubility parametervalues” by Eric A. Grulke in the “Polymer Handbook”, 3rd Edition,Chapter VII, pages 519-559, by the relationship:

δ=(δ_(d) ²+δ_(p) ²+δ_(h) ²)^(1/2)

in which relationship:

-   -   δ_(d) characterizes the London dispersion forces derived from        the formation of dipoles induced during molecular impacts, i.e.        nonpolar interactions,    -   δ_(p) characterizes the Debye interaction forces between        permanent dipoles,    -   δ_(h) characterizes the interaction forces of hydrogen bonding        type.

Thus, the Hansen solubility parameter δH takes into account thesolubility associated with the formation of hydrogen bonds in the liquidorganic compounds.

According to one embodiment, the liquid organic compound(s) have aHansen solubility parameter value δH ranging from 6 (MPa)^(1/2) to 14(MPa)^(1/2) at 25° C., and preferably ranging from 4 (MPa)^(1/2) to 10(MPa)^(1/2) at 25° C.

Preferably, the liquid organic compound(s) comprise a molecular weightof less than 500 g/mol and even more preferentially less than 250 g/mol.

Among the liquid organic compounds with a Hansen solubility parametervalue δH of less than 16 and particularly less than or equal to 15(MPa)^(1/2) at 25° C., mention may be made of propylene glycolderivatives, phenyl alcohols such as benzyl alcohol, alkylene carbonatesand lactones, in particular the lactones of formula (D1):

in which formula (D1):

-   -   n is 1,2 or 3;    -   R′ represents a hydrogen atom; a linear or branched C₁-C₈ alkyl        radical; a linear or branched C₁-C₄ hydroxyalkyl radical.

In accordance with an advantageous embodiment, the liquid organiccompound(s) with a Hansen solubility parameter value δH of less than 16(MPa)^(1/2) at 25° C. are chosen from the following compounds:

Name δH Benzyl alcohol 13.7 Dipropylene glycol methyl ether 11.2Tripropylene glycol methyl ether 10.4 Propylene glycol n-butyl ether(PnB) 9.2 Propylene glycol n-propyl ether (PnP) 9.2 Dipropylene glycolmonomethyl ether acetate 8 3-Phenyl-1-propanol 12.1 2-Phenyl-1-propanol12.9 Ethylene glycol 2-ethylhexyl ether 5.1 1-Octanol 11.9 1-Decanol 10Tridecyl alcohol 9 γ-Butyrolactone 7.4 Propylene carbonate 4.1

Preferably, the liquid organic compound(s) with a Hansen solubilityparameter value δH of less than 16 (MPa)^(1/2) at 25° C. are chosen fromalcohols, ethers and acids and/or a mixture of these compounds.

Preferably, the liquid organic compound(s) with a Hansen solubilityparameter value δH of less than 16 (MPa)^(1/2) at 25° C. are chosenfrom:

-   -   propylene glycol derivatives such as propylene glycol butyl        ether, dipropylene glycol methyl ether, tripropylene glycol        methyl ether or propylene glycol propyl ether, propylene glycol        n-butyl ether, dipropylene glycol monomethyl ether acetate;    -   aromatic alcohols, preferably phenyl alcohols such as benzyl        alcohol, 3-phenyl-1-propanol or 2-phenyl-1-ethanol;    -   alkylene carbonates;    -   lactones, in particular the lactones of formula (D1);    -   alcohols such as 1-Decanol or 1-Octanol;    -   ethers such as ethylene glycol 2-ethylhexyl ether;    -   and/or a mixture of these compounds.

Preferably, the liquid organic compound(s) with a Hansen solubilityparameter value δH of less than 16 (MPa)^(1/2) at 25° C. are chosen fromalcohols, aromatic alcohols, in particular from benzyl alcohol, ethers,propylene glycol derivatives, and/or a mixture of these compounds.

According to one embodiment, the liquid organic compound(s) with aHansen solubility parameter value δH of less than 16 (MPa)^(1/2) at 25°C. are chosen from alcohols.

In particular, the alcohol(s) that may be used as liquid organiccompounds with a Hansen solubility parameter δH as described above maybe chosen from aromatic alcohols, in particular from benzyl alcohol,3-phenyl-1-propanol and 2-phenyl-1-ethanol, and/or a mixture of thesecompounds.

According to one embodiment, the liquid organic compound(s) with aHansen solubility parameter value δH of less than 16 (MPa)^(1/2) at 25°C. are chosen from ethers.

In particular, the ethers that may be used as liquid organic compoundswith a Hansen solubility parameter δH as described above may bepropylene glycol butyl ether, dipropylene glycol methyl ether,tripropylene glycol methyl ether or propylene glycol propyl ether.

Preferably, the liquid organic compound(s) with a Hansen solubilityparameter value δH of less than 16 (MPa)^(1/2) at 25° C. are chosen frombenzyl alcohol, preferably benzyl alcohol.

The liquid organic compound(s) with a Hansen solubility parameter δH ofless than 16 (MPa)^(1/2) at 25° C. may be present in the compositioncontaining them in a content of greater than or equal to 0.5% by weight,preferably in a content of greater than or equal to 1% by weight, morepreferentially in a content ranging from 1% to 40% by weight and betterstill from 5% to 30% by weight relative to the total weight of thecomposition containing them.

e) Chemical Oxidizing Agent(s)

According to a particular embodiment of the invention, the dyeingprocess also uses one or more chemical oxidizing agents. The term“chemical oxidizing agent” means an oxidizing agent other thanatmospheric oxygen. More particularly, the dyeing process uses i)hydrogen peroxide; ii) urea peroxide; iii) polymeric complexes that canrelease hydrogen peroxide, such as polyvinylpyrrolidone/H₂O₂, providedin particular in the form of powders, and the other polymeric complexesdescribed in U.S. Pat. No. 5,008,093, U.S. Pat. No. 3,376,110 and U.S.Pat. No. 5,183,901; iv) oxidases in the presence of an appropriatesubstrate (for example, glucose in the case of glucose oxidase or uricacid with uricase); v) metal peroxides which generate hydrogen peroxidein water, such as calcium peroxide or magnesium peroxide; vi)perborates; and/or vii) percarbonates.

According to a preferred embodiment of the invention, the compositioncomprises one or more chemical oxidizing agents chosen from i) ureaperoxide; ii) polymeric complexes which can release hydrogen peroxidechosen from polyvinylpyrrolidone/H₂O₂; iii) oxidases; iv) perborates andv) percarbonates.

In particular, the dyeing process uses hydrogen peroxide.

Moreover, the composition(s) comprising hydrogen peroxide or a hydrogenperoxide-generating system may also include various adjuvantsconventionally used in compositions for dyeing keratin fibres as definedbelow.

According to a particular embodiment of the invention, the chemicaloxidizing agent(s) used preferably represent from 0.001% to 12% byweight of chemical oxidizing agents (of hydrogen peroxide) relative tothe total weight of the composition(s) containing it or them, and evenmore preferentially from 0.2% to 2.7% by weight.

f) Basifying Agent(s)

According to a particular embodiment of the invention, the dyeingprocess uses one or more basifying agents f). These are base(s) that canincrease the pH of the composition(s) in which they are present. Thebasifying agent is a Brønsted, Lowry or Lewis base. It may be mineral ororganic.

Particularly, said agent is chosen from i) (bi)carbonates, ii) aqueousammonia, iii) alkanolamines such as monoethanolamine, diethanolamine,triethanolamine and derivatives thereof, iv) oxyethylenated and/oroxypropylenated ethylenediamines, v) mineral or organic hydroxides, vi)alkali metal silicates such as sodium metasilicate, vii) amino acids,preferably basic amino acids such as arginine, lysine, ornithine,citrulline and histidine, and viii) the compounds of formula (XIII)below:

in which formula (XIII) W is a divalent (C₁-C₈)alkylene radicaloptionally substituted with at least one hydroxyl group or at least one(C₁-C₄)alkyl radical and/or optionally interrupted with at least oneheteroatom, such as oxygen or sulfur, or with an —N(R_(e))— group;R_(a), R_(b), R_(c), R_(d) and R_(e), which may be identical ordifferent, represent a hydrogen atom or a (C₁-C₄)alkyl orhydroxy(C₁-C₄)alkyl radical; preferably, W represents a propyleneradical. The mineral or organic hydroxides are preferably chosen from a)hydroxides of an alkali metal, b) hydroxides of an alkaline-earth metal,for instance sodium hydroxide or potassium hydroxide, c) hydroxides of atransition metal, such as hydroxides of metals from groups III, IV, Vand VI, d) hydroxides of lanthanides or actinides, quaternary ammoniumhydroxides and guanidinium hydroxide.

The hydroxide may be formed in situ, for instance guanidine hydroxide,formed by reacting calcium hydroxide with guanidine carbonate.

The term “(bi)carbonates” i) is understood to mean:

-   -   a) carbonates of alkali metals (Met₂ ⁺, CO₃ ²⁻), of        alkaline-earth metals (Met′²⁺, CO₃ ²⁻) of ammonium ((R″₄N⁺)₂,        CO₃ ²⁻) or of phosphonium ((R″₄P⁺)₂, CO₃ ²⁻ with Met′        representing an alkaline-earth metal and Met representing an        alkali metal, and R″, which may be identical or different,        represent a hydrogen atom or an optionally substituted        (C₁-C₆)alkyl group such as hydroxyethyl); and    -   b) bicarbonates, also known as hydrogen carbonates, of the        following formulae:        -   R′⁺, HCO₃ ⁻, with R′ representing a hydrogen atom, an alkali            metal, an ammonium group R″₄N⁺— or a phosphonium group            R″₄P⁺—, where R″, which may be identical or different,            represent a hydrogen atom or an optionally substituted            (C₁-C₆)alkyl group, such as hydroxyethyl, and, when R′            represents a hydrogen atom, the hydrogen carbonate is then            known as dihydrogen carbonate (CO₂, H₂O); and        -   Met′²⁺ (HCO₃ ⁻)₂, with Met′ representing an alkaline-earth            metal.

More particularly, the basifying agent is chosen from alkali metal oralkaline-earth metal (bi)carbonates and amino acids such as arginine;preferentially alkali metal (bi)carbonates and amino acids.

Mention may be made of Na, K, Mg and Ca carbonates or hydrogencarbonates and mixtures thereof, and in particular sodium hydrogencarbonate. These hydrogen carbonates may originate from a natural water,for example spring water from the Vichy basin or from La Roche-Posay orBadoit water (cf. patent, for example the document FR 2 814 943).Mention may in particular be made of sodium carbonate [497-19-8]=Na₂CO₃,sodium hydrogen carbonate or sodium bicarbonate [144-55-8]=NaHCO₃, andsodium dihydrogen carbonate=Na(HCO₃)₂.

According to a particularly advantageous embodiment, the basifyingagent(s) f) are chosen from amino acids, such as arginine, and(bi)carbonates, in particular alkali metal or alkaline-earth metal(bi)carbonates, alone or as mixtures. They are preferentially togetherduring the dyeing process.

The basifying agent(s) as defined above preferably represent from 0.001%to 10% by weight of the weight of the composition(s) containing them,more particularly from 0.005% to 8% by weight of the composition.

Water:

According to one embodiment of the invention, water is preferablyincluded in the process of the invention. It may originate from themoistening of the keratin fibres and/or from the composition(s)comprising compounds a) to e) as defined previously or from one or moreother compositions.

Preferably, the water originates at least from a composition comprisingat least one compound chosen from a) to f) as defined previously.

The Compositions:

The compositions according to the invention generally comprise water ora mixture of water and of one or more organic solvents or a mixture oforganic solvents.

The term “organic solvent” means an organic substance that is capable ofdissolving or dispersing another substance without chemically modifyingit.

The compositions according to the invention may optionally comprise anorganic solvent other than the liquid organic compound(s) which have aHansen solubility parameter value δH of less than 16 (MPa)^(1/2) at 25°C. d) as defined previously.

The Adjuvants:

The composition(s) of the dyeing process in accordance with theinvention may also contain various adjuvants conventionally used in hairdye compositions, such as anionic, cationic, nonionic, amphoteric orzwitterionic surfactants or mixtures thereof, anionic, cationic,nonionic, amphoteric or zwitterionic polymers or mixtures thereof otherthan the cellulose-based polysaccharides c) as defined previously,mineral or organic thickeners other than the cellulose-basedpolysaccharides c) as defined previously, and in particular anionic,cationic, nonionic and amphoteric polymeric associative thickeners,antioxidants, penetrants, sequestrants, fragrances, buffers,dispersants, conditioning agents, for instance volatile or non-volatile,modified or unmodified silicones, film-forming agents, ceramides,preserving agents and opacifiers.

The dyeing process of the invention may also use, in addition tocompounds a), b), optionally c) and optionally d), at least one otherparticular carboxylic acid of formula (I) as defined previously. Moreparticularly, the carboxylic acid(s) of formula (I) are such that Arepresents a monovalent (C₁-C₆)alkyl or polyvalent (C₁-C₆)alkylene groupoptionally substituted with one or more hydroxyl groups, and nrepresents an integer between 0 and 5, such as between 0 and 2,inclusive.

More particularly, the carboxylic acid(s) of the invention are chosenfrom the acids of formula (I) having a solubility in water of greaterthan or equal to 1% by weight at 25° C. and at atmospheric pressure.

Preferably, the acids of formula (I) comprise at least one hydroxylgroup in their structure. Even more preferentially, the acid is chosenfrom α-hydroxy acids. The preferred acids of the invention are chosenfrom glycolic acid, lactic acid, tartaric acid and citric acid.

The salts of the acids of formula (I) may be salts of organic or mineralbases, such as sodium hydroxide, aqueous ammonia or potassium hydroxide,or salts of organic amines, such as alkanolamines. The acids of formula(I) or salts thereof are present in the composition(s) containing themin a content ranging from 0.1% to 20% by weight.

Said adjuvants are preferably chosen from surfactants such as anionic ornonionic surfactants or mixtures thereof and mineral or organicthickeners.

The above adjuvants are generally present in an amount for each of themof between 0.01% and 40% by weight relative to the weight of thecomposition, and preferably between 0.1% and 20% by weight relative tothe weight of the composition.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compound(s) such that the advantageousproperties intrinsically associated with the composition(s) that areuseful in the dyeing process in accordance with the invention are not,or are not substantially, adversely affected by the envisagedaddition(s).

The cosmetic composition(s) of the invention may be in various galenicalforms, such as a powder, a lotion, a mousse, a cream or a gel, or in anyother form that is suitable for dyeing keratin fibres. They may also bepackaged in a propellant-free pump-action bottle or under pressure in anaerosol container in the presence of a propellant and form a foam.

pH of the Composition(s):

According to a preferred embodiment of the invention, the pH of at leastone of the cosmetic compositions comprising at least one of theingredients a), b), c), d) and e) is acidic, i.e. less than 7.0,preferably less than 5.0, in particular at a pH of between 0 and 4inclusive, more particularly between 0.5 and 3.5.

According to one embodiment, the pH of the cosmetic composition(s)comprising one or more alkaline agents preferably chosen from(bi)carbonates is alkaline, i.e. greater than 7, preferably of between 8and 12 and more particularly of between 8 and 10.5 inclusive.

When the process according to the invention uses one or more ODP dyes,the composition containing the ODP(s) a) preferably has an acidic pH ofless than 7, preferably less than 5, in particular a pH between 0 and 4inclusive and better still between 1 and 3.

According to a particular embodiment of the invention, the compositioncontaining the titanium salt(s) b) and not containing (bi)carbonates hasa pH of less than 7 and preferably of less than 5, in particular a pHbetween 0 and 4 inclusive, more particularly between 0.5 and 3.5.

The pH of these compositions may be adjusted to the desired value bymeans of basifying agents as defined previously in f) or by usingacidifying agents usually used in the dyeing of keratin fibres, oralternatively by means of standard buffer systems. Among the acidifyingagents for the compositions used in the invention, examples that may bementioned include mineral or organic acids, for instance hydrochloricacid, orthophosphoric acid, sulfuric acid, carboxylic acids, forinstance acetic acid, tartaric acid, citric acid or lactic acid, orsulfonic acids.

The term “carboxylic acid” means a compound comprising at least onecarboxylic acid —C(O)—OH group, preferably of formula (I) as definedpreviously, preferably comprising between 1 and 4 carboxylic acidgroups, such as 1 or 2; or chosen from: i) (C₁-C₁₀)alkyl-[C(O)—OH]_(n)and ii) het-[C(O)—OH]_(n), with n an integer between 1 and 4 inclusive,preferably between 1 and 2, het representing a heterocylic group, suchas pyrrolidone, it being possible for the alkyl or het group to beoptionally substituted with one or more groups chosen especially fromOH, and (di)(C₁-C₆)(alkyl)amino.

Dyeing Process in One or More Steps

The process for dyeing keratin fibres consists in treating, in one ormore steps, with one or more cosmetic compositions containing thefollowing ingredients, taken together or separately in saidcomposition(s):

-   -   a) one or more dyes chosen from synthetic direct dyes and dyes        of natural origin as defined previously, preferably chosen from        the ODPs as defined previously;    -   b) one or more titanium salts; optionally b1) one or more        carboxylic acids of formula (I) as defined previously;    -   c) one or more cellulose-based polysaccharides as defined        previously;    -   d) optionally one or more liquid organic compounds which have a        Hansen solubility parameter value δH of less than 16 (MPa)^(1/2)        at 25° C. and preferably less than or equal to 15 (MPa)^(1/2);    -   e) optionally one or more chemical oxidizing agents chosen        especially from hydrogen peroxide or one or more hydrogen        peroxide-generating systems;        preferably, the composition or at least one of the compositions        used in the dyeing process is at acidic pH, i.e. less than 7,        preferably less than 5, in particular at a pH of between 0 and 4        inclusive.

According to a particular embodiment of the invention, the dyeingprocess is performed in at least two steps which comprise a first stepin which the keratin fibres are treated with a cosmetic compositioncomprising a) one or more dyes chosen from synthetic direct dyes anddyes of natural origin, preferably one or more ODPs as definedpreviously, b) one or more titanium salts and optionally b1) one or morecarboxylic acids as defined previously, c) one or more cellulose-basedpolysaccharides as defined previously, and d) optionally one or moreliquid organic compounds with a Hansen solubility parameter value δH<16(MPa)^(1/2) at 25° C., preferably less than or equal to 15 (MPa)^(1/2);followed by a second step in which an alkaline cosmetic composition,i.e. a composition whose pH is greater than 7, preferably between 8 and12 and in particular between 8 and 10.5, which comprises e) one or morebasifying agents and optionally f) one or more chemical oxidizingagents, is applied.

Preferentially, the composition comprising a)+b)+c)+optionally d) andoptionally b1) and optionally e) is at acidic pH, i.e. less than 7,preferably less than 5, in particular at a pH of between 1 and 3inclusive.

Preferentially, the cosmetic composition applied to the keratin fibresduring the second step also comprises e) one or more chemical oxidizingagents chosen especially from hydrogen peroxide and one or more hydrogenperoxide-generating systems, preferably hydrogen peroxide.

The leave-on time after applying the composition comprising the dye(s),especially the ODP(s) as defined previously, is generally set at between3 and 120 minutes, preferentially between 10 and 60 minutes and morepreferentially between 15 and 45 minutes.

According to a particular embodiment of the invention, the process fordyeing keratin fibres is performed in two steps by applying to thekeratin fibres a dye composition comprising ingredients a), b), b1), c)and optionally d) as defined previously and then, in a second step, acomposition comprising ingredient e) and optionally ingredient f) asdefined previously is applied to said keratin fibres, it beingunderstood that at least one of the two compositions is aqueous.Preferably, the composition comprising the dye(s), especially the ODP(s)a) is aqueous. Even more preferentially, the two compositions used inthis embodiment are aqueous.

According to a particular embodiment of the invention, the dyeingprocess is performed in several steps by applying to the keratin fibres,in a first step, a cosmetic composition comprising:

-   a) one or more ODPs as defined previously, especially chosen from:

haematein, brazilein, gallic acid or tannic acid, when the dyeingprocess does not use a chemical oxidizing agent e);

or else

haematoxylin or brazilin, when the dyeing process uses a chemicaloxidizing agent e);

-   b) one or more organic titanium salts as defined previously;    advantageously, ingredient b) is chosen from Ti(IV) salts or    complexes; b1) optionally one or more carboxylic acids of    formula (I) as defined previously; and-   c) one or more cellulose-based polysaccharide(s) as defined    previously;-   d) optionally one or more organic compounds that are liquid at    25° C. with a solubility parameter value δH of less than 16    (MPa)^(1/2) at 25° C. as defined previously; and then, in a second    step, applying to said fibres a cosmetic composition comprising:-   e) optionally one or more chemical oxidizing agents chosen from    hydrogen peroxide or one or more hydrogen peroxide-generating    systems as defined previously; f) one or more basifying agents    chosen from amino acids and (bi)carbonates, in particular alkali    metal or alkaline-earth metal (bi)carbonates, alone or as a mixture;    it being understood that:

preferentially, the composition comprising a)+b)+c)+optionally d) andoptionally b1) is at acidic pH, i.e. less than 7, preferably less than5, in particular at a pH of between 1 and 3 inclusive; and

the composition comprising the basifying agent(s) is at alkaline pH,preferably of between 8 and 12 and more particularly of between 8 and10.

For this dyeing process, the leave-on time after application for thefirst step is generally set at between 3 and 120 minutes, preferentiallybetween 10 and 60 minutes and more preferentially between 15 and 45minutes. The application time of the composition comprising theingredient e) during the second step is generally set at between 3 and120 minutes, preferably between 3 and 60 minutes and more preferablybetween 5 and 30 minutes.

According to another embodiment, the process for dyeing keratin fibresis performed in two or three steps.

According to this embodiment, the process for dyeing keratin fibres isperformed in several steps by applying to the keratin fibres, in a firststep, a cosmetic composition comprising:

-   a) one or more dyes chosen from synthetic direct dyes and dyes of    natural origin, in particular one or more ODPs, especially chosen    from:    -   haematein, brazilein, gallic acid or tannic acid, when the        dyeing process does not use a chemical oxidizing agent e);

or else

-   -   haematoxylin or brazilin, when the dyeing process uses a        chemical oxidizing agent e);

-   b) one or more titanium salts as defined previously, and

-   b1) optionally one or more carboxylic acids of formula (I) as    defined previously with A representing a monovalent (C₁-C₆)alkyl or    polyvalent (C₁-C₆)alkylene group optionally substituted with one or    more hydroxyl groups, and n representing an integer between 0 and 5,    such as between 0 and 2, inclusive; more particularly, the    carboxylic acid or acids of the invention are chosen from citric    acid, lactic acid, glycolic acid and tartaric acid;    and then, in a second step, applying to said fibres a cosmetic    composition comprising:

-   c) one or more cellulose-based polysaccharides as defined    previously, which are particularly nonionic and non-associative,    preferably chosen from hydroxy(C₁-C₄)alkylcelluloses such as    hydroxyethylcelluloses (HEC);

-   d) optionally one or more liquid organic compounds with a Hansen    solubility parameter value δH of <16 (MPa)^(1/2) at 25° C.,    preferably chosen from aromatic alcohols such as benzyl alcohol;

-   e) optionally one or more chemical oxidizing agents chosen from    hydrogen peroxide or one or more hydrogen peroxide-generating    systems;

-   f) one or more basifying agent(s) chosen from amino acids, such as    arginine, and (bi)carbonates, in particular alkali metal or    alkaline-earth metal (bi)carbonates, alone or as mixtures;    it being understood that:    -   preferentially, the composition comprising a)+b) and optionally        b1) is at acidic pH, i.e. less than 7, preferably less than 5,        in particular at a pH of between 1 and 3 inclusive; and    -   the composition comprising the basifying agent(s) is at alkaline        pH, preferably of between 8 and 12 and more particularly of        between 8 and 10.

In particular, the dyeing process of the invention is performed in atleast two steps: in the first step, ingredients a), b) and c) andoptionally d) are applied together to the keratin fibres, in particularthe hair, and then, in the second step, ingredients e) and f) areapplied together to said fibres.

Irrespective of the application method, the application temperature isgenerally between room temperature (15 to 25° C.) and 220° C. and moreparticularly between 15 and 45° C. Thus, after application of thecomposition according to the invention, the head of hair mayadvantageously be subjected to a heat treatment by heating to atemperature of between 30 and 60° C. In practice, this operation may beperformed using a styling hood, a hairdryer, an infrared ray dispenseror other standard heating appliances.

Use may be made, both as means for heating and for smoothing the head ofhair, of a heating iron at a temperature of between 60° C. and 220° C.and preferably between 120° C. and 200° C.

Irrespective of the application method, it is possible to performrinsing or mechanical wiping and/or drying of the keratin fibres betweeneach step, in particular before performing the final step comprising theapplication of a composition containing the ingredient e).

The steps of intermediate mechanical wiping and drying are also known as“controlled non-rinsing” to distinguish from “standard abundant rinsingwith water” and “non-rinsing”. The term “mechanical wiping” of thefibres means rubbing an absorbent article on the fibres and physicalremoval, by means of the absorbent article, of the excess ingredient(s)that have not penetrated the fibres. The absorbent article may be apiece of fabric such as a towel, particularly a terry towel, a cloth orabsorbent paper such as household roll towel.

According to a particularly advantageous process of the invention, themechanical wiping is performed without total drying of the fibre,leaving the fibre moist.

The term “drying” means the action of evaporating the organic solventsand/or water present in one or more compositions used in the process ofthe invention, comprising or not comprising one or more ingredients a)to e) as defined previously. The drying may be performed with a sourceof heat (convection, conduction or radiation) by sending, for example, astream of hot gas such as air necessary to evaporate the solvent(s).Sources of heat that may be mentioned include a hairdryer, a hairstylinghood, a hair-straightening iron, an infrared ray dispenser or otherstandard heating appliances.

A particular embodiment of the invention relates to a dyeing processwhich is performed at room temperature (25° C.).

In all the particular forms and variants of the processes previouslydescribed, the compositions mentioned are ready-to-use compositions thatmay result from the extemporaneous mixing of two or more compositionsand in particular of compositions present in dyeing kits.

Dyeing Device or “Kit”

Another subject of the invention is a multi-compartment dyeing device or“kit”. Advantageously, this kit comprises from 2 to 5 compartmentscomprising from 2 to 5 compositions in which are distributed theingredients a) to e) as defined above, which can be aqueous orpulverulent, with in particular at least one of said compositions beingaqueous.

According to a first variant, the kit comprises five compartments, thefirst four compartments respectively comprising ingredients a), b), c)and f) as defined previously and the fifth compartment containing anaqueous oxidizing composition, such as water comprising e) as definedpreviously. Optionally, d) and/or b1) are preferably contained with a).

In this other embodiment, at least one of the four compositions isaqueous and the dye(s), in particular the ODP(s), may be in powder form.

In another kit variant, this kit comprises two compartments, in whichthe first composition contained in the first compartment comprises a),b) and c) and the second compartment comprises e) in powder form or inaqueous medium; preferably, the second composition is aqueous.

In another kit variant, this kit comprises four compartments, in whichthe first composition contained in the first compartment comprises a),the second compartment comprises b), the third compartment comprises e)and the fourth compartment comprises f).

Compound c) may be in any compartment, but preferably with a). Compoundd) is preferably with a), and compound b1) is preferably with b).

In another kit variant, this kit comprises three compartments, in whichthe first composition contained in the first compartment comprises a),the second compartment comprises e) in powder form or in aqueous medium;preferably, the second composition is aqueous and the third compartmentcomprises f).

Compound b) may be in any compartment, but preferably with a). Compoundb) is with a) or e) and preferably with a). Compound d) is preferablywith a).

According to a particular embodiment of the invention, the kit comprisesfive separate compartments in which the first compartment contains a)one or more dyes chosen from synthetic direct dyes and dyes of naturalorigin, preferably chosen from the ODPs as defined previously, thesecond compartment contains b) the Ti salt(s) as defined previously, andoptionally b1) one or more carboxylic acids as defined previously, thethird compartment contains c) one or more cellulose-basedpolysaccharides as defined previously, the fourth compartment containse) one or more chemical oxidizing agents as defined previously,especially hydrogen peroxide, and a fifth compartment comprises f) oneor more alkaline agents, it being understood that the solvent d) asdefined previously may optionally be in at least one of the fivecompartments.

According to a particular embodiment of the invention, the kit comprisesfour separate compartments in which the first compartment contains a)one or more dyes chosen from synthetic direct dyes and dyes of naturalorigin, preferably chosen from the ODPs as defined previously, thesecond compartment contains b) the Ti salt(s) as defined previously, andoptionally b1) one or more carboxylic acids as defined previously, thethird compartment contains e) one or more chemical oxidizing agents asdefined previously, especially hydrogen peroxide, and a fourthcompartment comprises f) one or more alkaline agents, it beingunderstood that:

-   -   c) one or more cellulose-based polysaccharides as defined        previously are in at least one of the four compartments, and    -   the solvent d) as defined previously may optionally be in at        least one of the four compartments.

According to a particular embodiment of the invention, the kit comprisesthree separate compartments in which the first compartment contains a)one or more dyes chosen from synthetic direct dyes and dyes of naturalorigin, preferably chosen from the ODPs as defined previously, thesecond compartment contains e) one or more chemical oxidizing agents asdefined previously, especially hydrogen peroxide, and a thirdcompartment comprises f) one or more alkaline agents, it beingunderstood that:

-   -   b) the Ti salt(s) as defined previously, and optionally b1) one        or more carboxylic acids as defined previously, are with the        dye(s) or with the chemical oxidizing agent(s), in particular        H₂O₂; preferably, the Ti salt(s) are with the dye(s),    -   c) one or more cellulose-based polysaccharides as defined        previously are in at least one of the three compartments,        preferably with the dye(s), and    -   the solvent d) as defined previously may optionally be in at        least one of the three compartments.

According to one variant, the device according to the invention alsocomprises an additional composition comprising one or more treatingagents.

The compositions of the device according to the invention are packagedin separate compartments, optionally accompanied by suitable applicationmeans which may be identical or different, such as fine brushes, coarsebrushes or sponges.

The device mentioned above may also be equipped with a means fordispensing the desired mixture on the hair, for instance the devicesdescribed in patent FR 2 586 913.

A subject of the invention is also the use of said cosmetic dyecomposition for dyeing keratin fibres.

A subject of the invention is also a cosmetic composition for dyeingkeratin fibres, containing compounds a), b), b1), c), d) and e) asdefined previously.

For the purposes of the present invention, the term “build-up” of thecolour of keratin fibres means the variation in colouring between locksof undyed grey hair and locks of dyed hair.

The example that follows serves to illustrate the invention without,however, being limiting in nature.

EXAMPLES OF DYEING Example 1

The following compositions are prepared from the following ingredientsin the following proportions, indicated in grams per 100 grams ofcomposition:

Dyeing Composition:

Com- Ingredients position 1 Composition 2 Composition 3 Haematoxylin, a)4 g 4 g 4 g sold by Sigma CAS = 517-28-2 Dihydroxybis(ammonium 12.1 g12.1 g 12.1 g lactato) titanium(IV) at 50% by weight: b) 19495-50-8Lactic acid b1) 10.1 g 10.1 g 10.1 g Hydroxyethylcellulose 1.6 g — —(HEC) c) sold under the name Natrosol 250 Mr by Ashland HEC c) soldunder — 1.4 g 1.2 g the name Natrosol 250 HHR CS by Ashland Ethanol 15 g15 g 15 g Xanthan gum sold — — 0.4 g under the name Rhodicare XC byRhodia Water qs 100 g qs 100 g qs 100 g pH agent qs pH = 2 ± 0.2

Developing Composition:

Composition B Amount Aqueous hydrogen peroxide solution (50%): e) 2.4 gL-Arginine: f) 7 g Sodium bicarbonate: f) 5 g Hydroxypropyl starchphosphate sold under the 5 g name Structure Zea by Akzo Nobel Water qs100 g pH agent pH 10 ± 0.3The dye compositions 1 to 3 and then composition B are applied with abrush to permanent-waved Caucasian hair containing 90% white hairs.

Compositions 1 to 3 are then left on for a time of 45 minutes at 40° C.and composition B is left on for a time of 15 minutes at 40° C. Rinsingis performed before applying composition B.

After these leave-on times, the locks are washed with ElviveMultivitamin shampoo, rinsed and then dried under a hood.

Dyeing Results

It is found that very strongly coloured black locks are obtained, whichis corroborated by the colorimetric measurements below. In addition, itis seen that the colouring is visually homogeneous and persistent withrespect to successive shampooing.

The colour of the locks was evaluated in the CIE L*a*b* system using aMinolta Spectrophotometer CM3600D colorimeter. In this L*a*b* system,the three parameters denote, respectively, the colour intensity (L*),the green/red colour axis (a*) and the blue/yellow colour axis (b*).

Colour Build-Up:

The variation in colouring between the locks of permanent-wavedCaucasian hair containing 90% white hairs, before and after treatment ordyeing, is defined by (ΔE*) according to the following equation:

ΔE*=√{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b _(o)*)²)}

In this equation, L*, a* and b* represent the values measured on locksof hair after dyeing and L₀*, a₀* and b₀* represent the values measuredon locks of undyed virgin hair. The higher the ΔE* value, the better thecolour build-up.

The results L, a, b of colour build-up are collated in the table below:

ΔE* Types of hair and treatment Colour L* a* b* build-up Composition 1then B Natural permanent-waved Black 22.16 1.97 2.39 42.9 Caucasian, 90%white hairs Composition 2 then B Natural permanent-waved Black 21.992.32 2.51 43.04 Caucasian, 90% white hairs Composition 3 then B Naturalpermanent-waved Black 21.16 1.88 1.86 44.01 Caucasian, 90% white hairs

After the keratin fibres have been treated with compositions 1 to 3, thelocks obtained are a very strong and intense black.

Example 2

The following dye compositions are prepared according to the sameprotocol as in Example 1:

Dyeing Composition:

Ingredients Composition 4 Composition 5 Disperse Red 13, a) 3180-81-20.5 g HC Violet 2: 2-N- — 0.5 g hydroxypropylamino-5-N,N-bis(b-hydroxyethyl)aminonitrobenzene a) Glycolic acid b1) 15 g 15 gDihydroxybis(ammonium lactato) 10.3 g 10.3 g titanium(IV) at 50% byweight: b) HEC sold under the name Natrosol 1.2 g — 250 HHR CS byAshland, c) HEC sold under the name Natrosol — 1 g 250 Mr by Ashland, c)Ethanol 15 g 15 g Benzyl alcohol d) 5 g 5 g Water qs 100 g qs 100 g pHagent qs pH = 2 ± 0.2

Very strongly coloured red locks (composition 4) and violet locks(composition 5) are obtained.

1.-20. (canceled)
 21. A method for dyeing keratin fibers, comprisingapplying to the fibers a composition comprising: a) at least one dyechosen from synthetic direct dyes and/or dyes of natural origin; b) atleast one titanium salt; b1) optionally, at least one carboxylic acidaccording to formula (I) below, or salts thereof:

wherein: A is chosen from a monovalent group when n is 0 or a polyvalentgroup when n is greater than or equal to 1; or a saturated orunsaturated, cyclic or non-cyclic and aromatic or non-aromatichydrocarbon-based group comprising from 1 to 50 carbon atoms which isoptionally interrupted with at least one heteroatom and/or optionallysubstituted; and n is an integer ranging from 0 to 10; c) at least onecellulose-based polysaccharide; d) optionally, at least one organiccompound that is liquid at 25° C. with a Hansen solubility parametervalue δH of less than 16 (MPa)^(1/2) at 25° C.; and e) optionally, atleast one chemical oxidizing agent chosen from hydrogen peroxide or atleast one hydrogen peroxide-generating system.
 22. The method accordingto claim 21, wherein the at least one dye is an ortho-diphenolcomprising an aromatic ring, wherein the aromatic ring is chosen frombenzene, naphthalene, tetrahydronaphthalene, indane, indene, anthracene,phenanthrene, isoindole, indoline, isoindoline, benzofuran,dihydrobenzofuran, chroman, isochroman, chromene, isochromene,quinoline, tetrahydroquinoline, or isoquinoline, wherein the aromaticring comprises at least two hydroxyl groups borne by two contiguousadjacent atoms of the aromatic ring.
 23. The method according to claim21, wherein the at least one dye is an ortho-diphenol according toformula (II) below, oligomers, tautomers, optical isomers, geometricalisomers thereof, salts, solvates, or hydrates thereof:

wherein: R¹ to R⁴, which may be identical or different, are chosen from:i) hydrogen, ii) halogen atoms, iii) hydroxyl groups, iv) carboxylgroups, v) (C₁-C₂₀)alkyl carboxylate or (C₁-C₂₀)alkoxycarbonyl groups,vi) optionally substituted amino groups, vii) optionally substitutedlinear or branched (C₁-C₂₀)alkyl groups, viii) optionally substitutedlinear or branched (C₂-C₂₀)alkenyl groups, ix) optionally substitutedcycloalkyl groups, x) (C₁-C₂₀)alkoxy groups, xi)(C₁-C₂₀)alkoxy(C₁-C₂₀)alkyl groups, xii) (C₁-C₂₀)alkoxyaryl groups,xiii) aryl groups which may optionally be substituted, xiv) aryl groups,xv) substituted aryl groups, xvi) heterocyclic groups which aresaturated or unsaturated, optionally bearing a cationic or anioniccharge and which are optionally substituted and/or optionally fused withan aromatic ring, the aromatic ring optionally substituted, or xvii)radical groups containing at least one silicon atom; or, optionally: twoof the substituents borne by two adjacent carbon atoms R¹-R², R²-R³ orR³-R⁴ optionally form, together with the carbon atoms bearing them, asaturated or unsaturated, aromatic or non-aromatic ring optionallycontaining at least one heteroatom and optionally fused with at leastone saturated or unsaturated ring optionally containing at least oneheteroatom; R¹ to R⁴ together form from one to four rings; or R² and R³form a pyrrolyl or pyrrolidinyl radical fused to the benzene ringbearing the two hydroxyls.
 24. The method according to claim 21, whereinthe at least one dye is an ortho-diphenol chosen from: flavanols;anthocyanidins; anthocyanins or anthocyans; ortho-hydroxybenzoates;flavones; hydroxystilbenes; 3,4-dihydroxyphenylalanine or derivativesthereof; 2,3-dihydroxyphenylalanine or derivatives thereof;4,5-dihydroxyphenylalanine or derivatives thereof; dihydroxycinnamates;ortho-polyhydroxycoumarins; ortho-polyhydroxyisocoumarins;ortho-polyhydroxycoumarones; ortho-polyhydroxyisocoumarones;ortho-polyhydroxychalcones; ortho-polyhydroxychromones; quinones;hydroxyxanthones; 1,2-dihydroxybenzene or derivatives thereof;1,2,4-trihydroxybenzene or derivatives thereof; 1,2,3-trihydroxybenzeneor derivatives thereof; 2,4,5-trihydroxytoluene or derivatives thereof;proanthocyanidins; chromans or chromenes; proanthocyanins; tannic acid;ellagic acid; or mixtures thereof.
 25. The method according to claim 21,wherein the at least one dye is an ortho-diphenol chosen from extractsof animals, bacteria, fungi, algae, plants, or fruit.
 26. The methodaccording to claim 21, wherein the composition comprises at least onecarboxylic acid is chosen from compounds according to formula (I)wherein A is chosen from monovalent (C₁-C₆)alkyl groups or polyvalent(C₁-C₆)alkylene groups optionally substituted with at least one hydroxylgroup, and n is an integer ranging from 0 to
 5. 27. The method accordingto claim 21, wherein the composition comprises at least one carboxylicacid present in an amount ranging from about 0.1% to about 20% byweight, relative to the total weight of the composition.
 28. The methodaccording to claim 21, wherein the at least one titanium salt is chosenfrom organic or mineral titanium salts.
 29. The method according toclaim 28, wherein the organic titanium salts are derived from thereaction of at least one organic acid with titanium, wherein the atleast one organic acid is chosen from organic acids comprising: a) atleast one optionally unsaturated, linear or branched C₁-C₂₀hydrocarbon-based chain, or a (hetero)cycloalkyl or (hetero)aryl group;and b) at least one acid chemical function chosen from carboxyl COOH,sulfuric SO₃H, SO₂H, or phosphoric PO₃H₂, PO₄H₂.
 30. The methodaccording to claim 29, wherein the composition comprises at least onecarboxylic acid represented by formula (I), and wherein the at least onecarboxylic acid is different from the at least one organic acid that theorganic titanium salt is derived from.
 31. The method according to claim28, wherein the organic titanium salts are chosen from compoundsaccording to formula (I-A) below:

wherein: A is chosen from a monovalent group when n is 0 or a polyvalentgroup when n is greater than or equal to 1; or a saturated orunsaturated, cyclic or non-cyclic and aromatic or non-aromatichydrocarbon-based group comprising from 1 to 50 carbon atoms which isoptionally interrupted with at least one heteroatom and/or optionallysubstituted; n, n′, and n″, which may be identical or different, areintegers chosen from 1, 2, 3, or 4, wherein n′+n″=6; M₁ and M₂, whichmay be identical or different, are chosen from a cationic counterion;and TiY_(n″), is chosen from Ti(OH)_(n″), Ti(O)_(n″/2), orTi(OH)_(m1)(O)_(m2) with m₁+m₂=n″.
 32. The method according to claim 28,wherein the organic titanium salts are dihydroxybis(lactato)titanium(IV)salts according to the formula below:


33. The method according to claim 21, wherein the at least onecellulose-based polysaccharide is chosen from associative ornon-associative anionic, cationic, amphoteric, or nonionic polymers. 34.The method according to claim 21, wherein the composition comprises atleast one organic compound chosen from organic solvents, such organicsolvents chosen from: propylene glycol derivatives; aromatic alcohols;alkylene carbonates; lactones according to formula (D1) below:

wherein: n is equal to 1, 2 or 3; and R′ is chosen from hydrogen atom; alinear or branched C₁-C₈ alkyl radical; or a linear or branched C₁-C₄hydroxyalkyl radical; alcohols; ethers; or mixtures thereof.
 35. Themethod according to claim 21, wherein the composition comprises at leastone organic compoundchosen from alcohols, aromatic alcohols, benzylalcohol, ethers, propylene glycol derivatives, or mixtures thereof. 36.The method according to claim 21, wherein the composition comprises atleast one chemical oxidizing agent chosen from hydrogen peroxide or atleast one hydrogen peroxide-generating system.
 37. The method accordingto claim 21, further comprising applying at least one basifying agent tothe hair, said basifying agent chosen from: i) (bi)carbonates; ii)aqueous ammonia; iii) alkanolamines; iv) oxyethylenated and/oroxypropylenated ethylenediamines; v) mineral or organic hydroxides; vi)alkali metal silicates; vii) amino acids; or viii) the compoundsaccording to formula (XIII) below:

wherein: W is a divalent (C₁-C₈)alkylene radical optionally substitutedwith at least one hydroxyl group or at least one (C₁-C₄)alkyl radicaland/or optionally interrupted with at least one heteroatomor with agroup —N(R_(e))—; and R_(a), R_(b), R_(c), R_(d), and R_(e), which maybe identical or different, are chosen from hydrogen, a (C₁-C₄)alkyl orhydroxy(C₁-C₄)alkyl radical, or mixtures thereof.
 38. The methodaccording to claim 21, wherein the composition has a pH of less than 7.39. The method according to claim 21, comprising: applying to thekeratin fibers a dyeing composition comprising a) at least one dyechosen from synthetic direct dyes and/or dyes of natural origin; b) atleast one titanium salt; b1) optionally, at least one carboxylic acidaccording to formula (I) below, or salts thereof:

wherein: A is chosen from a monovalent group when n is 0 or a polyvalentgroup when n is greater than or equal to 1; or a saturated orunsaturated, cyclic or non-cyclic and aromatic or non-aromatichydrocarbon-based group comprising from 1 to 50 carbon atoms which isoptionally interrupted with at least one heteroatom and/or optionallysubstituted; and n is an integer ranging from 0 to 10; c) at least onecellulose-based polysaccharide; and d) optionally, at least one organiccompound that is liquid at 25° C. with a Hansen solubility parametervalue δH of less than 16 (MPa)^(1/2) at 25° C.; wherein the dyeingcomposition has a pH of less than 7; and e) optionally, at least onechemical oxidizing agent chosen from hydrogen peroxide or at least onehydrogen peroxide-generating system; and f) at least one basifyingagent; wherein the alkaline composition has a pH greater than
 7. 40. Acosmetic composition for dyeing keratin fibers, comprising: a) at leastone dye chosen from synthetic direct dyes and/or dyes of natural origin;b) at least one titanium salt; b1) optionally, at least one carboxylicacid according to formula (I) below, or salts thereof:

wherein: A is chosen from a monovalent group when n is 0 or a polyvalentgroup when n is greater than or equal to 1; or a saturated orunsaturated, cyclic or non-cyclic and aromatic or non-aromatichydrocarbon-based group comprising from 1 to 50 carbon atoms which isoptionally interrupted with at least one heteroatom and/or optionallysubstituted; and n is an integer ranging from 0 to 10; c) at least onecellulose-based polysaccharide; d) optionally, at least one organiccompound that is liquid at 25° C. with a Hansen solubility parametervalue δH of less than 16 (MPa)^(1/2) at 25° C.; and e) optionally, atleast one chemical oxidizing agent chosen from hydrogen peroxide or atleast one hydrogen peroxide-generating system.
 41. A multi-compartmentdevice comprising from 2 to 5 compartments containing from 2 to 5compositions, the device comprising: a) at least one dye chosen fromsynthetic direct dyes and/or dyes of natural origin; b) at least onetitanium salt; b1) optionally, at least one carboxylic acid according toformula (I) below, or salts thereof:

wherein: A is chosen from a monovalent group when n is 0 or a polyvalentgroup when n is greater than or equal to 1; or a saturated orunsaturated, cyclic or non-cyclic and aromatic or non-aromatichydrocarbon-based group comprising from 1 to 50 carbon atoms which isoptionally interrupted with at least one heteroatom and/or optionallysubstituted; and n is an integer ranging from 0 to 10; c) optionally, atleast one cellulose-based polysaccharide; d) optionally, at least oneorganic compound that is liquid at 25° C. with a Hansen solubilityparameter value δH of less than 16 (MPa)^(1/2) at 25° C.; and e)optionally, at least one chemical oxidizing agent chosen from hydrogenperoxide or at least one hydrogen peroxide-generating system; wherein atleast one compartment further comprises water.